Distortions of a flexible metal-organic framework from substituted pendant ligands

Four new variants of the 1,4-benzenedicarboxylate MIL-53 structure have been prepared for Co^II under solvothermal conditions and their structures solved and refined from single-crystal X-ray data. All materials contain pendant pyridine-N-oxide ligands that bridge pairs of Co^II atoms in the inorganic backbone of the structure via O. By the use of the ligands 3-bromopyridine-N-oxide, 4-methoxypyridine-N-oxide, isoquinoline-N-oxide and 4-phenylpyridine-N-oxide, materials are prepared with the same topology but distinct structures. These illustrate how the MIL-53 structure is able to distort to accommodate the bulk of the various substituents on the pyridine ring. The bulkiest pendant ligand, 4-phenylpyridine-N-oxide, results in a distortion of the diamond-shaped channels in an opposite sense to that seen previously in expanded forms of the parent MIL-53 structure. By comparison with published crystal structures for MIL-53 with various occluded guests, the structural distortions that take place to accommodate the pendant ligands are quantified and it is shown how a twisting of the 1,4-benzenedicarboxylate ligand, instead of a hinging about the μ²-carboxylate-metal connection, allows the new structures that are observed.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006) for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; CrystalClear-SM (Rigaku, 2011) for Co-BDC-isoquiniline. Cell refinement: CrysAlis RED, (Oxford Diffraction, 2006) for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; CrystalClear-SM for Co-BDC-isoquiniline. Data reduction: CrysAlis RED for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; CrystalClear-SM for Co-BDC-isoquiniline. Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; SHELXL2013 for Co-BDC-isoquiniline. Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; SHELXL2013 (Sheldrick, 2008) for Co-BDC-isoquiniline. Molecular graphics: SHELXTL (Sheldrick, 2008) for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; OLEX2 (Dolomanov et al., 2009) for Co-BDC-isoquiniline. Software used to prepare material for publication: SHELXTL for Co-BDC-3-Br-PNO, Co-BDC-4-methyoxy-PNO, Co-BDC-4-phenyl-PNO; OLEX2 for Co-BDC-isoquiniline.

Figures

(Co-BDC-3-Br-PNO)

Crystal data

C13H8BrCoNO5	F(000) = 780
Mr = 397.04	Dx = 1.944 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1138 reflections
a = 7.1962 (8) Å	θ = 3.3–30.8°
b = 10.0563 (13) Å	µ = 4.23 mm^−1
c = 18.748 (3) Å	T = 296 K
β = 91.548 (12)°	Block, pink
V = 1356.3 (3) Å^3	0.20 × 0.04 × 0.03 mm
Z = 4

Data collection

Oxford Diffraction Gemini R diffractometer	3637 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1444 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.138
Detector resolution: 10.2833 pixels mm^-1	θmax = 30.9°, θmin = 3.5°
φ & ω scans	h = −9→9
Absorption correction: multi-scan ABSPACK (Oxford Diffraction, 2006)	k = −14→10
Tmin = 0.62, Tmax = 1.00	l = −26→17
6996 measured 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)] = 0.104	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.289	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.1268P)^2] where P = (Fo^2 + 2Fc^2)/3
3637 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.79 e Å^−3
54 restraints	Δρmin = −1.46 e Å^−3

Special details

Experimental. A small crystal was mounted on the glass fibre with silicon grease and the data recorded at room temperature. The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of four sets of exposures with different φ angles for the crystal; each 100 s exposure covered 1.0° in ω. The crystal-to-detector distance was 5.5 cm. Crystal decay was found to be negligible by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they are attached. The bromopyridine ring had large cigar shaped elipsoids. Attempts at refining a disordered model with two bromopyridine ring positions did not give a satisfactory refinement so SIMU restraints were used to give the atoms of this ring more reasonable thermal parameters.

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
Co1	−0.5000	0.5000	0.5000	0.0208 (5)
Co2	0.0000	0.5000	0.5000	0.0216 (5)
O1	−0.1070 (8)	0.6558 (7)	0.4394 (3)	0.0277 (15)
O2	−0.4131 (8)	0.6340 (7)	0.4249 (3)	0.0346 (16)
C2	−0.2582 (12)	0.6674 (9)	0.4034 (5)	0.0250 (17)
C3	−0.2520 (11)	0.7294 (10)	0.3305 (5)	0.026 (2)
C4	−0.4137 (12)	0.7512 (14)	0.2914 (5)	0.045 (3)
H4	−0.5274	0.7293	0.3107	0.054*
C5	−0.4093 (13)	0.8053 (13)	0.2236 (5)	0.049 (3)
H5	−0.5200	0.8178	0.1978	0.058*
C6	−0.2433 (12)	0.8410 (10)	0.1937 (5)	0.027 (2)
C7	−0.0830 (13)	0.8267 (13)	0.2352 (5)	0.052 (4)
H7	0.0301	0.8558	0.2180	0.062*
C8	−0.0903 (12)	0.7691 (12)	0.3023 (5)	0.038 (3)
H8	0.0197	0.7573	0.3287	0.046*
O9	−0.3917 (8)	0.8924 (8)	0.0838 (3)	0.0375 (18)
C9	−0.2393 (12)	0.8894 (10)	0.1175 (5)	0.026 (2)
O10	−0.0837 (8)	0.9204 (7)	0.0949 (3)	0.0334 (17)
O11	−0.2488 (7)	0.3928 (6)	0.4868 (3)	0.0234 (15)
N12	−0.2450 (11)	0.2659 (11)	0.4844 (6)	0.050 (2)
C13	−0.2658 (14)	0.1949 (12)	0.5441 (8)	0.055 (3)
H13	−0.2871	0.2394	0.5866	0.067*
Br14	−0.2821 (3)	−0.0329 (2)	0.62917 (14)	0.1247 (10)
C14	−0.2569 (16)	0.0591 (14)	0.5446 (8)	0.063 (3)
C15	−0.2397 (17)	−0.0041 (16)	0.4840 (9)	0.076 (3)
H15	−0.2392	−0.0965	0.4833	0.091*
C16	−0.2217 (18)	0.0680 (16)	0.4191 (9)	0.077 (3)
H16	−0.2089	0.0233	0.3761	0.093*
C17	−0.2236 (16)	0.2019 (14)	0.4209 (8)	0.067 (3)
H17	−0.2105	0.2504	0.3791	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0186 (8)	0.0256 (10)	0.0182 (9)	0.0005 (8)	0.0029 (6)	0.0001 (8)
Co2	0.0218 (9)	0.0267 (11)	0.0165 (9)	0.0024 (8)	0.0028 (6)	−0.0008 (9)
O1	0.028 (3)	0.028 (3)	0.027 (3)	−0.002 (3)	−0.008 (2)	0.005 (3)
O2	0.028 (3)	0.041 (4)	0.035 (4)	0.000 (3)	0.004 (3)	0.009 (3)
C2	0.031 (4)	0.017 (4)	0.027 (4)	0.002 (3)	0.003 (3)	0.004 (3)
C3	0.024 (4)	0.025 (5)	0.029 (5)	−0.001 (4)	0.000 (3)	0.001 (4)
C4	0.015 (5)	0.094 (10)	0.027 (6)	−0.006 (5)	0.003 (4)	0.020 (6)
C5	0.018 (5)	0.097 (11)	0.031 (6)	0.000 (6)	−0.003 (4)	0.021 (7)
C6	0.033 (5)	0.031 (6)	0.017 (5)	0.004 (4)	−0.002 (4)	0.012 (4)
C7	0.026 (5)	0.102 (11)	0.027 (6)	−0.019 (6)	−0.003 (4)	0.019 (7)
C8	0.022 (5)	0.064 (8)	0.028 (6)	−0.002 (5)	−0.004 (4)	0.010 (5)
O9	0.028 (3)	0.058 (5)	0.027 (4)	0.000 (3)	−0.001 (3)	0.016 (4)
C9	0.020 (5)	0.025 (5)	0.034 (6)	0.007 (4)	0.000 (4)	−0.004 (5)
O10	0.023 (3)	0.053 (5)	0.024 (4)	−0.004 (3)	0.008 (3)	0.013 (3)
O11	0.018 (3)	0.014 (3)	0.038 (4)	0.003 (3)	0.006 (3)	0.000 (3)
N12	0.032 (4)	0.043 (5)	0.076 (6)	0.003 (4)	−0.009 (4)	−0.008 (4)
C13	0.034 (4)	0.044 (5)	0.088 (6)	−0.002 (4)	−0.006 (5)	0.008 (5)
Br14	0.1058 (14)	0.0737 (13)	0.194 (3)	−0.0049 (10)	−0.0060 (14)	0.0708 (15)
C14	0.041 (5)	0.049 (6)	0.099 (7)	−0.008 (5)	−0.009 (5)	0.009 (5)
C15	0.060 (5)	0.057 (6)	0.110 (8)	−0.005 (5)	−0.010 (6)	−0.008 (6)
C16	0.066 (5)	0.065 (6)	0.100 (7)	0.003 (5)	−0.009 (5)	−0.021 (6)
C17	0.052 (5)	0.060 (6)	0.088 (7)	0.010 (5)	−0.006 (5)	−0.019 (5)

Geometric parameters (Å, º)

Co1—O9^i	2.044 (6)	C6—C7	1.381 (12)
Co1—O9^ii	2.044 (6)	C6—C9	1.510 (12)
Co1—O2^iii	2.059 (6)	C7—C8	1.389 (13)
Co1—O2	2.059 (6)	C7—H7	0.9300
Co1—O11^iii	2.125 (5)	C8—H8	0.9300
Co1—O11	2.125 (5)	O9—C9	1.252 (9)
Co2—O10^i	2.057 (6)	O9—Co1^vi	2.044 (6)
Co2—O10^iv	2.057 (6)	C9—O10	1.247 (10)
Co2—O1^v	2.072 (6)	O10—Co2^vii	2.057 (6)
Co2—O1	2.072 (6)	O11—N12	1.277 (12)
Co2—O11	2.099 (5)	N12—C13	1.340 (16)
Co2—O11^v	2.099 (5)	N12—C17	1.366 (15)
O1—C2	1.270 (10)	C13—C14	1.367 (17)
O2—C2	1.241 (10)	C13—H13	0.9300
C2—C3	1.504 (13)	Br14—C14	1.848 (15)
C3—C8	1.351 (12)	C14—C15	1.31 (2)
C3—C4	1.377 (12)	C15—C16	1.42 (2)
C4—C5	1.382 (13)	C15—H15	0.9300
C4—H4	0.9300	C16—C17	1.35 (2)
C5—C6	1.381 (13)	C16—H16	0.9300
C5—H5	0.9300	C17—H17	0.9300
O9^i—Co1—O9^ii	180.0000 (10)	C5—C4—H4	119.6
O9^i—Co1—O2^iii	86.4 (3)	C6—C5—C4	121.2 (8)
O9^ii—Co1—O2^iii	93.6 (3)	C6—C5—H5	119.4
O9^i—Co1—O2	93.6 (3)	C4—C5—H5	119.4
O9^ii—Co1—O2	86.4 (3)	C7—C6—C5	117.6 (9)
O2^iii—Co1—O2	180.0000 (10)	C7—C6—C9	122.0 (8)
O9^i—Co1—O11^iii	87.1 (2)	C5—C6—C9	120.5 (8)
O9^ii—Co1—O11^iii	92.9 (2)	C6—C7—C8	120.2 (9)
O2^iii—Co1—O11^iii	88.7 (2)	C6—C7—H7	119.9
O2—Co1—O11^iii	91.3 (2)	C8—C7—H7	119.9
O9^i—Co1—O11	92.9 (2)	C3—C8—C7	122.2 (9)
O9^ii—Co1—O11	87.1 (2)	C3—C8—H8	118.9
O2^iii—Co1—O11	91.3 (2)	C7—C8—H8	118.9
O2—Co1—O11	88.7 (2)	C9—O9—Co1^vi	135.4 (6)
O11^iii—Co1—O11	180.0 (3)	O10—C9—O9	127.2 (9)
O10^i—Co2—O10^iv	180.00 (16)	O10—C9—C6	116.2 (8)
O10^i—Co2—O1^v	86.2 (3)	O9—C9—C6	116.6 (8)
O10^iv—Co2—O1^v	93.8 (3)	C9—O10—Co2^vii	132.6 (6)
O10^i—Co2—O1	93.8 (3)	N12—O11—Co2	119.9 (5)
O10^iv—Co2—O1	86.2 (3)	N12—O11—Co1	122.0 (5)
O1^v—Co2—O1	180.0 (3)	Co2—O11—Co1	116.8 (3)
O10^i—Co2—O11	91.9 (2)	O11—N12—C13	120.1 (11)
O10^iv—Co2—O11	88.1 (2)	O11—N12—C17	120.3 (11)
O1^v—Co2—O11	88.8 (2)	C13—N12—C17	119.6 (12)
O1—Co2—O11	91.2 (2)	N12—C13—C14	122.2 (14)
O10^i—Co2—O11^v	88.1 (2)	N12—C13—H13	118.9
O10^iv—Co2—O11^v	91.9 (2)	C14—C13—H13	118.9
O1^v—Co2—O11^v	91.2 (2)	C15—C14—C13	118.9 (16)
O1—Co2—O11^v	88.8 (2)	C15—C14—Br14	121.0 (12)
O11—Co2—O11^v	180.00 (14)	C13—C14—Br14	120.0 (13)
C2—O1—Co2	131.4 (6)	C14—C15—C16	120.4 (16)
C2—O2—Co1	133.7 (6)	C14—C15—H15	119.8
O2—C2—O1	124.6 (9)	C16—C15—H15	119.8
O2—C2—C3	117.1 (8)	C17—C16—C15	119.1 (16)
O1—C2—C3	118.3 (8)	C17—C16—H16	120.4
C8—C3—C4	117.9 (9)	C15—C16—H16	120.4
C8—C3—C2	121.7 (8)	C16—C17—N12	119.6 (16)
C4—C3—C2	120.3 (8)	C16—C17—H17	120.2
C3—C4—C5	120.8 (8)	N12—C17—H17	120.2
C3—C4—H4	119.6

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x−1, y−1/2, −z+1/2; (iii) −x−1, −y+1, −z+1; (iv) −x, y−1/2, −z+1/2; (v) −x, −y+1, −z+1; (vi) −x−1, y+1/2, −z+1/2; (vii) −x, y+1/2, −z+1/2.

(Co-BDC-4-methyoxy-PNO)

Crystal data

C14H11CoNO6	F(000) = 708
Mr = 348.17	Dx = 1.531 Mg m^−3
Orthorhombic, Pnma	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -p 2ac 2n	Cell parameters from 2929 reflections
a = 7.1507 (2) Å	θ = 3.8–70.6°
b = 18.1353 (4) Å	µ = 9.18 mm^−1
c = 11.6447 (3) Å	T = 100 K
V = 1510.09 (7) Å^3	Block, pink
Z = 4	0.36 × 0.06 × 0.06 mm

Data collection

Oxford Diffraction Gemini R diffractometer	1496 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1426 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 10.2833 pixels mm^-1	θmax = 70.7°, θmin = 4.5°
φ & ω scans	h = −5→8
Absorption correction: multi-scan ABSPACK (Oxford Diffraction, 2006)	k = −22→20
Tmin = 0.44, Tmax = 1.00	l = −14→13
7235 measured 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0698P)^2 + 3.5094P] where P = (Fo^2 + 2Fc^2)/3
1496 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.95 e Å^−3
25 restraints	Δρmin = −0.39 e Å^−3

Special details

Experimental. The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cobra. The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of 17 sets of exposures with different φ angles for the crystal; each 10 s low angle and 40 s high angle exposure covered 1.0° in ω. The crystal-to-detector distance was 5.5 cm. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 (or 1.5 for methyl H-atoms) times the equivalent isotropic displacement parameter of the atom to which they are attached.

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. The 4-methoxypyridine N-oxide was disordered about the mirror plane. It was constrained to be a hexagon using AFIX 66 and refined at half occupancy under a PART -1 instruction (two components refined at 50:50 occupancy about the mirror plane). The thermal parameters of some of the terephthalate ligands were rather elongated and subjected to a SIMU restraint. Co1 and O6 lie on the mirror plane and the terephthalate lies on an inversion centre.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.22106 (9)	0.7500	0.24179 (5)	0.0103 (2)
O1	0.1264 (4)	0.66666 (16)	0.3479 (3)	0.0389 (7)
O2	−0.1838 (4)	0.66827 (15)	0.3686 (3)	0.0342 (6)
C2	−0.0250 (5)	0.6408 (2)	0.3801 (4)	0.0342 (7)
C3	−0.0135 (5)	0.5673 (2)	0.4425 (4)	0.0353 (8)
C4	0.1395 (7)	0.5221 (3)	0.4274 (6)	0.0661 (19)
H4	0.2366	0.5367	0.3765	0.079*
C5	−0.1530 (7)	0.5442 (3)	0.5145 (6)	0.0666 (19)
H5	−0.2607	0.5742	0.5247	0.080*
O6	−0.0343 (4)	0.7500	0.1599 (3)	0.0193 (7)
N7	−0.0485 (5)	0.7414 (2)	0.0481 (3)	0.0255 (14)	0.50
C8	−0.0432 (9)	0.8029 (2)	−0.0233 (3)	0.033 (3)	0.50
H8	−0.0297	0.8507	0.0088	0.039*	0.50
C9	−0.0578 (9)	0.7942 (2)	−0.1415 (3)	0.029 (2)	0.50
H9	−0.0542	0.8362	−0.1903	0.035*	0.50
C10	−0.0776 (7)	0.7242 (3)	−0.1885 (3)	0.029 (2)	0.50
C11	−0.0828 (10)	0.6628 (2)	−0.1172 (3)	0.0309 (18)	0.50
H11	−0.0963	0.6149	−0.1493	0.037*	0.50
C12	−0.0683 (9)	0.6714 (2)	0.0011 (3)	0.029 (2)	0.50
H12	−0.0719	0.6294	0.0498	0.035*	0.50
O13	−0.0922 (9)	0.7116 (4)	−0.3012 (5)	0.0444 (15)	0.50
C14	−0.0802 (12)	0.7739 (5)	−0.3774 (7)	0.046 (3)	0.50
H14A	−0.0996	0.7575	−0.4567	0.069*	0.50
H14B	0.0436	0.7966	−0.3705	0.069*	0.50
H14C	−0.1765	0.8100	−0.3569	0.069*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0100 (4)	0.0071 (4)	0.0139 (4)	0.000	0.0005 (2)	0.000
O1	0.0186 (11)	0.0382 (13)	0.0600 (16)	−0.0035 (10)	−0.0008 (11)	0.0364 (12)
O2	0.0191 (11)	0.0322 (13)	0.0514 (15)	0.0060 (10)	0.0042 (11)	0.0295 (11)
C2	0.0169 (11)	0.0338 (13)	0.0519 (14)	0.0013 (10)	0.0013 (11)	0.0292 (12)
C3	0.0171 (14)	0.0349 (16)	0.0539 (18)	0.0019 (13)	0.0014 (14)	0.0284 (15)
C4	0.031 (2)	0.064 (3)	0.103 (5)	0.012 (2)	0.026 (3)	0.059 (3)
C5	0.032 (2)	0.059 (3)	0.109 (5)	0.021 (2)	0.025 (3)	0.060 (3)
O6	0.0123 (16)	0.0335 (19)	0.0122 (15)	0.000	0.0002 (12)	0.000
N7	0.012 (2)	0.049 (4)	0.015 (2)	0.002 (4)	0.0005 (17)	−0.016 (4)
C8	0.019 (4)	0.052 (7)	0.028 (5)	−0.003 (4)	0.002 (3)	−0.009 (5)
C9	0.028 (4)	0.035 (6)	0.024 (5)	−0.006 (4)	−0.005 (4)	0.009 (4)
C10	0.019 (4)	0.048 (6)	0.020 (4)	0.004 (3)	−0.004 (3)	0.000 (3)
C11	0.034 (4)	0.031 (5)	0.028 (4)	0.004 (4)	−0.003 (3)	−0.010 (4)
C12	0.027 (5)	0.042 (6)	0.018 (4)	0.006 (4)	0.007 (3)	−0.010 (4)
O13	0.040 (3)	0.077 (4)	0.016 (3)	−0.005 (3)	−0.001 (3)	−0.006 (3)
C14	0.033 (4)	0.086 (9)	0.020 (4)	−0.005 (4)	−0.002 (3)	0.004 (4)

Geometric parameters (Å, º)

Co1—O6	2.060 (3)	O6—N7	1.315 (4)
Co1—O1^i	2.066 (2)	O6—Co1^iv	2.091 (3)
Co1—O1	2.066 (2)	N7—C8	1.3900
Co1—O2^ii	2.077 (2)	N7—C12	1.3900
Co1—O2^iii	2.077 (2)	C8—C9	1.3900
Co1—O6^iii	2.091 (3)	C8—H8	0.9500
O1—C2	1.239 (5)	C9—C10	1.3900
O2—C2	1.247 (5)	C9—H9	0.9500
O2—Co1^iv	2.077 (2)	C10—O13	1.337 (7)
C2—C3	1.519 (5)	C10—C11	1.3900
C3—C5	1.369 (6)	C11—C12	1.3900
C3—C4	1.379 (7)	C11—H11	0.9500
C4—C5^v	1.384 (6)	C12—H12	0.9500
C4—H4	0.9500	O13—C14	1.439 (10)
C5—C4^v	1.384 (6)	C14—H14A	0.9800
C5—H5	0.9500	C14—H14B	0.9800
O6—N7^i	1.315 (4)	C14—H14C	0.9800
O6—Co1—O1^i	89.23 (10)	C3—C5—H5	119.5
O6—Co1—O1	89.23 (10)	C4^v—C5—H5	119.5
O1^i—Co1—O1	94.0 (2)	N7^i—O6—Co1	121.8 (3)
O6—Co1—O2^ii	90.22 (10)	N7—O6—Co1	121.8 (3)
O1^i—Co1—O2^ii	87.44 (13)	N7^i—O6—Co1^iv	118.5 (3)
O1—Co1—O2^ii	178.43 (14)	N7—O6—Co1^iv	118.5 (3)
O6—Co1—O2^iii	90.22 (10)	Co1—O6—Co1^iv	119.22 (15)
O1^i—Co1—O2^iii	178.43 (14)	O6—N7—C8	119.7 (2)
O1—Co1—O2^iii	87.44 (13)	O6—N7—C12	120.4 (2)
O2^ii—Co1—O2^iii	91.09 (19)	C8—N7—C12	120.0
O6—Co1—O6^iii	174.38 (9)	N7—C8—C9	120.0
O1^i—Co1—O6^iii	86.93 (10)	N7—C8—H8	120.0
O1—Co1—O6^iii	86.93 (10)	C9—C8—H8	120.0
O2^ii—Co1—O6^iii	93.71 (10)	C8—C9—C10	120.0
O2^iii—Co1—O6^iii	93.71 (10)	C8—C9—H9	120.0
C2—O1—Co1	138.1 (2)	C10—C9—H9	120.0
C2—O2—Co1^iv	130.6 (2)	O13—C10—C11	116.6 (4)
O1—C2—O2	127.7 (3)	O13—C10—C9	123.4 (4)
O1—C2—C3	115.5 (3)	C11—C10—C9	120.0
O2—C2—C3	116.8 (3)	C10—C11—C12	120.0
C5—C3—C4	118.3 (4)	C10—C11—H11	120.0
C5—C3—C2	121.5 (4)	C12—C11—H11	120.0
C4—C3—C2	120.2 (4)	C11—C12—N7	120.0
C3—C4—C5^v	120.6 (4)	C11—C12—H12	120.0
C3—C4—H4	119.7	N7—C12—H12	120.0
C5^v—C4—H4	119.7	C10—O13—C14	117.8 (6)
C3—C5—C4^v	121.0 (4)

Symmetry codes: (i) x, −y+3/2, z; (ii) x+1/2, −y+3/2, −z+1/2; (iii) x+1/2, y, −z+1/2; (iv) x−1/2, y, −z+1/2; (v) −x, −y+1, −z+1.

(Co-BDC-isoquiniline)

Crystal data

C17H11CoNO5·0.25(O)	F(000) = 758
Mr = 372.70	Dx = 1.606 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
a = 18.025 (16) Å	θ = 2.0–27.5°
b = 7.184 (6) Å	µ = 1.14 mm^−1
c = 11.906 (11) Å	T = 100 K
V = 1542 (2) Å^3	Needle, orange
Z = 4	0.25 × 0.02 × 0.01 mm

Data collection

Rigaku AFC12 Saturn CCD diffractometer	1671 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	Rint = 0.057
profile data from ω–scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan CrystalClear-SM (Rigaku, 2011)	h = −23→19
Tmin = 0.566, Tmax = 1.000	k = −9→7
7338 measured reflections	l = −15→15
1867 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.090	H-atom parameters constrained
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + 15.6918P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
1867 reflections	Δρmax = 0.53 e Å^−3
154 parameters	Δρmin = −0.75 e Å^−3
0 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.5000	0.5000	0.5000	0.0141 (2)
O1	0.4077 (2)	0.5945 (6)	0.5862 (4)	0.0436 (12)
C2	0.3795 (4)	0.7500	0.6053 (6)	0.0209 (15)
C3	0.3051 (4)	0.7500	0.6632 (6)	0.0209 (15)
C4	0.2796 (11)	0.908 (3)	0.7179 (14)	0.036 (4)	0.5
H4	0.3094	1.0172	0.7130	0.043*	0.5
C5	0.2133 (12)	0.921 (4)	0.7802 (16)	0.039 (5)	0.5
H5	0.1977	1.0328	0.8159	0.047*	0.5
C4A	0.2614 (9)	0.912 (3)	0.6722 (15)	0.034 (4)	0.5
H4A	0.2765	1.0245	0.6365	0.040*	0.5
C5A	0.1965 (12)	0.906 (3)	0.7333 (16)	0.037 (4)	0.5
H5A	0.1681	1.0169	0.7396	0.045*	0.5
C6	0.1711 (4)	0.7500	0.7850 (6)	0.0216 (15)
C7	0.0986 (4)	0.7500	0.8528 (7)	0.0245 (16)
O8	0.0727 (2)	0.9057 (6)	0.8770 (4)	0.0396 (11)
O9	0.4900 (3)	0.2500	0.5878 (4)	0.0174 (10)
N10	0.4861 (4)	0.2500	0.7019 (5)	0.0229 (13)
C11	0.5475 (5)	0.2500	0.7614 (7)	0.0319 (19)
H11	0.5945	0.2500	0.7254	0.038*
C12	0.5424 (6)	0.2500	0.8814 (7)	0.041 (2)
C13	0.6072 (8)	0.2500	0.9466 (10)	0.082 (5)
H13	0.6541	0.2500	0.9103	0.098*
C14	0.6043 (11)	0.2500	1.0599 (10)	0.095 (6)
H14	0.6488	0.2500	1.1027	0.114*
C15	0.5350 (9)	0.2500	1.1138 (9)	0.070 (4)
H15	0.5325	0.2500	1.1936	0.084*
C16	0.4711 (8)	0.2500	1.0520 (8)	0.063 (4)
H16	0.4244	0.2500	1.0889	0.076*
C17	0.4744 (7)	0.2500	0.9339 (8)	0.044 (2)
C18	0.4112 (7)	0.2500	0.8651 (9)	0.063 (3)
H18	0.3632	0.2500	0.8981	0.076*
C19	0.4183 (6)	0.2500	0.7511 (9)	0.057 (3)
H19	0.3751	0.2500	0.7054	0.068*
O10	0.694 (3)	0.7500	0.461 (4)	0.106 (15)*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0137 (4)	0.0129 (4)	0.0156 (4)	−0.0001 (4)	−0.0001 (3)	−0.0006 (4)
O1	0.041 (2)	0.025 (2)	0.065 (3)	0.011 (2)	0.034 (2)	0.012 (2)
C2	0.020 (3)	0.027 (4)	0.017 (3)	0.000	0.010 (3)	0.000
C3	0.022 (3)	0.023 (4)	0.018 (3)	0.000	0.008 (3)	0.000
C4	0.039 (10)	0.025 (7)	0.044 (11)	−0.003 (7)	0.006 (7)	0.014 (9)
C5	0.039 (10)	0.029 (9)	0.049 (12)	0.003 (7)	0.018 (8)	−0.008 (10)
C4A	0.030 (9)	0.023 (7)	0.047 (11)	0.003 (7)	0.017 (7)	0.014 (9)
C5A	0.040 (10)	0.011 (6)	0.061 (13)	0.001 (7)	0.029 (9)	−0.005 (10)
C6	0.029 (4)	0.012 (3)	0.023 (4)	0.000	0.007 (3)	0.000
C7	0.028 (4)	0.023 (4)	0.022 (4)	0.000	0.006 (3)	0.000
O8	0.049 (2)	0.023 (2)	0.046 (3)	0.0134 (19)	0.038 (2)	0.007 (2)
O9	0.029 (3)	0.012 (2)	0.011 (2)	0.000	0.0025 (19)	0.000
N10	0.036 (4)	0.015 (3)	0.018 (3)	0.000	0.001 (3)	0.000
C11	0.039 (5)	0.034 (5)	0.023 (4)	0.000	−0.006 (3)	0.000
C12	0.074 (7)	0.024 (4)	0.026 (4)	0.000	−0.019 (5)	0.000
C13	0.075 (9)	0.131 (14)	0.040 (6)	0.000	−0.021 (6)	0.000
C14	0.143 (15)	0.116 (14)	0.026 (6)	0.000	−0.018 (8)	0.000
C15	0.149 (14)	0.038 (6)	0.022 (5)	0.000	−0.020 (7)	0.000
C16	0.120 (11)	0.047 (6)	0.022 (5)	0.000	0.015 (6)	0.000
C17	0.079 (7)	0.028 (5)	0.025 (5)	0.000	0.005 (5)	0.000
C18	0.067 (7)	0.091 (10)	0.031 (5)	0.000	0.018 (5)	0.000
C19	0.032 (5)	0.101 (10)	0.037 (5)	0.000	0.013 (4)	0.000

Geometric parameters (Å, º)

Co1—O1	2.070 (4)	C7—O8^iv	1.246 (5)
Co1—O1^i	2.070 (4)	C7—O8	1.246 (5)
Co1—O8^ii	2.079 (4)	O8—Co1^v	2.079 (4)
Co1—O8^iii	2.079 (4)	O9—Co1^vi	2.086 (3)
Co1—O9	2.086 (3)	O9—N10	1.361 (7)
Co1—O9^i	2.086 (3)	N10—C11	1.314 (10)
O1—C2	1.248 (5)	N10—C19	1.355 (11)
C2—O1^iv	1.248 (5)	C11—H11	0.9500
C2—C3	1.508 (9)	C11—C12	1.432 (12)
C3—C4^iv	1.39 (2)	C12—C13	1.403 (15)
C3—C4	1.39 (2)	C12—C17	1.376 (15)
C3—C4A^iv	1.41 (2)	C13—H13	0.9500
C3—C4A	1.41 (2)	C13—C14	1.349 (16)
C4—H4	0.9500	C14—H14	0.9500
C4—C5	1.41 (3)	C14—C15	1.41 (2)
C5—H5	0.9500	C15—H15	0.9500
C5—C6	1.45 (2)	C15—C16	1.367 (19)
C4A—H4A	0.9500	C16—H16	0.9500
C4A—C5A	1.38 (3)	C16—C17	1.407 (13)
C5A—H5A	0.9500	C17—C18	1.403 (16)
C5A—C6	1.36 (2)	C18—H18	0.9500
C6—C5^iv	1.45 (2)	C18—C19	1.364 (14)
C6—C5A^iv	1.36 (2)	C19—H19	0.9500
C6—C7	1.536 (10)
O1—Co1—O1^i	180.0 (2)	C5A—C6—C5A^iv	111.2 (17)
O1—Co1—O8^ii	87.1 (2)	C5A^iv—C6—C7	121.7 (9)
O1^i—Co1—O8^ii	92.9 (2)	C5A—C6—C7	121.7 (9)
O1—Co1—O8^iii	92.9 (2)	O8^iv—C7—C6	116.1 (4)
O1^i—Co1—O8^iii	87.1 (2)	O8—C7—C6	116.1 (4)
O1^i—Co1—O9	92.01 (17)	O8^iv—C7—O8	127.7 (7)
O1—Co1—O9	87.99 (17)	C7—O8—Co1^v	133.8 (4)
O1^i—Co1—O9^i	87.99 (17)	Co1^vi—O9—Co1	118.9 (2)
O1—Co1—O9^i	92.01 (17)	N10—O9—Co1^vi	120.32 (11)
O8^ii—Co1—O8^iii	180.0	N10—O9—Co1	120.32 (11)
O8^ii—Co1—O9	91.02 (18)	C11—N10—O9	119.6 (7)
O8^iii—Co1—O9	88.98 (18)	C11—N10—C19	121.8 (8)
O8^ii—Co1—O9^i	88.98 (18)	C19—N10—O9	118.5 (7)
O8^iii—Co1—O9^i	91.02 (18)	N10—C11—H11	120.5
O9—Co1—O9^i	180.0	N10—C11—C12	118.9 (9)
C2—O1—Co1	135.3 (4)	C12—C11—H11	120.5
O1^iv—C2—O1	127.1 (7)	C13—C12—C11	119.9 (11)
O1^iv—C2—C3	116.4 (3)	C17—C12—C11	120.7 (9)
O1—C2—C3	116.4 (3)	C17—C12—C13	119.3 (10)
C4—C3—C2	120.5 (9)	C12—C13—H13	119.3
C4^iv—C3—C2	120.5 (9)	C14—C13—C12	121.4 (15)
C4^iv—C3—C4	110.0 (17)	C14—C13—H13	119.3
C4A—C3—C2	122.1 (8)	C13—C14—H14	120.3
C4A^iv—C3—C2	122.1 (8)	C13—C14—C15	119.4 (15)
C4A^iv—C3—C4A	111.5 (16)	C15—C14—H14	120.3
C3—C4—H4	117.3	C14—C15—H15	119.9
C3—C4—C5	125 (2)	C16—C15—C14	120.2 (11)
C5—C4—H4	117.3	C16—C15—H15	119.9
C4—C5—H5	122.9	C15—C16—H16	119.9
C4—C5—C6	114.2 (19)	C15—C16—C17	120.2 (13)
C6—C5—H5	122.9	C17—C16—H16	119.9
C3—C4A—H4A	120.4	C12—C17—C16	119.4 (12)
C5A—C4A—C3	119.1 (18)	C12—C17—C18	117.2 (8)
C5A—C4A—H4A	120.4	C18—C17—C16	123.3 (12)
C4A—C5A—H5A	118.2	C17—C18—H18	119.8
C6—C5A—C4A	123.6 (18)	C19—C18—C17	120.4 (11)
C6—C5A—H5A	118.2	C19—C18—H18	119.8
C5^iv—C6—C5	116.4 (19)	N10—C19—C18	120.9 (11)
C5^iv—C6—C7	117.9 (10)	N10—C19—H19	119.5
C5—C6—C7	117.9 (10)	C18—C19—H19	119.5

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, z−1/2; (iii) x+1/2, −y+3/2, −z+3/2; (iv) x, −y+3/2, z; (v) x−1/2, −y+3/2, −z+3/2; (vi) −x+1, y−1/2, −z+1.

(Co-BDC-4-phenyl-PNO)

Crystal data

C19H13CoNO5	F(000) = 804
Mr = 394.23	Dx = 1.749 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 1307 reflections
a = 12.9936 (8) Å	θ = 4.5–70.3°
b = 17.9026 (8) Å	µ = 9.30 mm^−1
c = 7.1797 (4) Å	T = 100 K
β = 116.294 (8)°	Needle, yellow
V = 1497.32 (16) Å^3	0.12 × 0.02 × 0.02 mm
Z = 4

Data collection

Oxford Diffraction Gemini R diffractometer	1404 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1264 reflections with I > 2˘I)
Graphite monochromator	Rint = 0.040
Detector resolution: 10.2833 pixels mm^-1	θmax = 70.5°, θmin = 4.5°
φ & ω scans	h = −15→14
Absorption correction: multi-scan ABSPACK(Oxford Diffraction, 2006)	k = −21→19
Tmin = 0.43, Tmax = 1.00	l = −8→7
3151 measured 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0598P)^2] where P = (Fo^2 + 2Fc^2)/3
1404 reflections	(Δ/σ)max < 0.001
122 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

Experimental. The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cobra. The data collection nominally covered over a hemisphere of Reciprocal space, by a combination of fifteen sets of exposures with different φ angles for the crystal; each 12 s low angle exposure and 48 s high angle exposure covered 1.0 ° in ω. The crystal-to-detector distance was 5.5 cm. Crystal decay was found to be negligible by by repeating the initial frames at the end of data collection and analyzing the duplicate reflections. Hydrogen atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H-atoms were given isotropic displacement parameter equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they are attached.

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
Co1	0.5000	0.0000	0.0000	0.01012 (19)
O1	0.60170 (14)	0.08775 (10)	0.1862 (2)	0.0153 (4)
C2	0.64355 (18)	0.10289 (14)	0.3759 (4)	0.0139 (5)
C3	0.7008 (2)	0.17830 (15)	0.4404 (4)	0.0183 (5)
O4	0.64022 (13)	0.06302 (9)	0.5180 (3)	0.0151 (4)
C4	0.6533 (2)	0.24064 (15)	0.3120 (4)	0.0184 (5)
H4	0.5867	0.2346	0.1837	0.022*
C5	0.7979 (2)	0.18898 (15)	0.6300 (4)	0.0191 (5)
H5	0.8306	0.1477	0.7200	0.023*
O6	0.5000	−0.05720 (13)	0.2500	0.0147 (5)
N7	0.5000	−0.13221 (16)	0.2500	0.0140 (6)
C8	0.4023 (2)	−0.16891 (15)	0.2079 (4)	0.0173 (5)
H8	0.3338	−0.1418	0.1765	0.021*
C9	0.4009 (2)	−0.24579 (15)	0.2099 (4)	0.0191 (5)
H9	0.3316	−0.2712	0.1836	0.023*
C10	0.5000	−0.2872 (2)	0.2500	0.0149 (7)
C11	0.5000	−0.3696 (2)	0.2500	0.0164 (7)
C12	0.4016 (2)	−0.41010 (15)	0.2196 (4)	0.0199 (6)
H12	0.3337	−0.3840	0.1992	0.024*
C13	0.4013 (2)	−0.48719 (16)	0.2186 (5)	0.0229 (6)
H13	0.3335	−0.5137	0.1965	0.028*
C14	0.5000	−0.5260 (2)	0.2500	0.0254 (8)
H14	0.5000	−0.5790	0.2500	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0100 (3)	0.0078 (3)	0.0130 (3)	−0.00014 (18)	0.0056 (2)	0.00011 (19)
O1	0.0171 (8)	0.0141 (9)	0.0143 (8)	−0.0047 (6)	0.0067 (7)	−0.0023 (7)
C2	0.0105 (10)	0.0126 (12)	0.0195 (12)	−0.0030 (8)	0.0075 (9)	−0.0003 (9)
C3	0.0167 (11)	0.0208 (13)	0.0215 (13)	−0.0039 (9)	0.0122 (10)	−0.0035 (10)
O4	0.0125 (7)	0.0156 (9)	0.0166 (8)	−0.0031 (6)	0.0060 (7)	0.0000 (7)
C4	0.0169 (11)	0.0190 (13)	0.0188 (12)	−0.0017 (10)	0.0075 (10)	−0.0019 (10)
C5	0.0190 (12)	0.0168 (12)	0.0224 (13)	−0.0004 (10)	0.0100 (10)	−0.0007 (10)
O6	0.0207 (11)	0.0070 (11)	0.0174 (11)	0.000	0.0094 (10)	0.000
N7	0.0182 (13)	0.0088 (14)	0.0140 (13)	0.000	0.0062 (11)	0.000
C8	0.0149 (12)	0.0151 (13)	0.0216 (12)	0.0004 (9)	0.0077 (10)	−0.0015 (9)
C9	0.0156 (12)	0.0157 (13)	0.0256 (13)	−0.0020 (9)	0.0088 (10)	−0.0012 (10)
C10	0.0155 (15)	0.0136 (17)	0.0146 (16)	0.000	0.0057 (13)	0.000
C11	0.0164 (15)	0.0150 (18)	0.0160 (16)	0.000	0.0057 (13)	0.000
C12	0.0149 (12)	0.0154 (13)	0.0270 (13)	−0.0002 (9)	0.0071 (10)	−0.0012 (10)
C13	0.0171 (13)	0.0177 (13)	0.0327 (15)	−0.0048 (10)	0.0098 (12)	−0.0024 (11)
C14	0.0239 (18)	0.0107 (18)	0.038 (2)	0.000	0.0102 (17)	0.000

Geometric parameters (Å, º)

Co1—O6^i	2.0665 (12)	O6—Co1^ii	2.0665 (12)
Co1—O6	2.0665 (12)	N7—C8	1.339 (3)
Co1—O4^ii	2.0977 (16)	N7—C8^ii	1.339 (3)
Co1—O4^iii	2.0977 (16)	C8—C9	1.377 (4)
Co1—O1	2.1062 (16)	C8—H8	0.9500
Co1—O1^i	2.1062 (16)	C9—C10	1.401 (3)
O1—C2	1.253 (3)	C9—H9	0.9500
C2—O4	1.261 (3)	C10—C9^ii	1.401 (3)
C2—C3	1.512 (3)	C10—C11	1.476 (5)
C3—C5	1.399 (4)	C11—C12	1.400 (3)
C3—C4	1.405 (4)	C11—C12^ii	1.400 (3)
O4—Co1^ii	2.0977 (16)	C12—C13	1.380 (4)
C4—C5^iv	1.389 (4)	C12—H12	0.9500
C4—H4	0.9500	C13—C14	1.386 (3)
C5—C4^iv	1.389 (4)	C13—H13	0.9500
C5—H5	0.9500	C14—C13^ii	1.386 (3)
O6—N7	1.343 (4)	C14—H14	0.9500
O6^i—Co1—O6	180.00 (11)	C3—C5—H5	119.6
O6^i—Co1—O4^ii	90.81 (6)	N7—O6—Co1^ii	119.70 (6)
O6—Co1—O4^ii	89.19 (6)	N7—O6—Co1	119.70 (6)
O6^i—Co1—O4^iii	89.19 (6)	Co1^ii—O6—Co1	120.59 (11)
O6—Co1—O4^iii	90.81 (6)	C8—N7—C8^ii	121.2 (3)
O4^ii—Co1—O4^iii	180.00 (11)	C8—N7—O6	119.38 (15)
O6^i—Co1—O1	86.57 (6)	C8^ii—N7—O6	119.38 (15)
O6—Co1—O1	93.43 (6)	N7—C8—C9	120.3 (2)
O4^ii—Co1—O1	85.50 (6)	N7—C8—H8	119.9
O4^iii—Co1—O1	94.50 (6)	C9—C8—H8	119.9
O6^i—Co1—O1^i	93.43 (6)	C8—C9—C10	121.0 (2)
O6—Co1—O1^i	86.57 (6)	C8—C9—H9	119.5
O4^ii—Co1—O1^i	94.50 (6)	C10—C9—H9	119.5
O4^iii—Co1—O1^i	85.50 (6)	C9^ii—C10—C9	116.1 (3)
O1—Co1—O1^i	180.00 (6)	C9^ii—C10—C11	121.93 (16)
C2—O1—Co1	134.40 (15)	C9—C10—C11	121.93 (16)
O1—C2—O4	127.1 (2)	C12—C11—C12^ii	117.7 (3)
O1—C2—C3	116.3 (2)	C12—C11—C10	121.14 (17)
O4—C2—C3	116.5 (2)	C12^ii—C11—C10	121.14 (17)
C5—C3—C4	118.3 (2)	C13—C12—C11	121.2 (2)
C5—C3—C2	121.9 (2)	C13—C12—H12	119.4
C4—C3—C2	119.7 (2)	C11—C12—H12	119.4
C2—O4—Co1^ii	126.47 (15)	C12—C13—C14	120.0 (3)
C5^iv—C4—C3	120.9 (2)	C12—C13—H13	120.0
C5^iv—C4—H4	119.5	C14—C13—H13	120.0
C3—C4—H4	119.5	C13^ii—C14—C13	119.9 (4)
C4^iv—C5—C3	120.7 (3)	C13^ii—C14—H14	120.1
C4^iv—C5—H5	119.6	C13—C14—H14	120.1

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, y, −z+1/2; (iii) x, −y, z−1/2; (iv) −x+3/2, −y+1/2, −z+1.