The structure of {[Co(pht)(bpy)(H2O)]·3H2O}n (pht is phthalate and bpy is 4,4′-bi­pyridine) and the role of solvent water clusters in structure stability

Harvey, M.A.; Suarez, S.; Doctorovich, F.; Cukiernik, F.D.; Baggio, R.

doi:10.1107/S2053229614006950

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The structure of {[Co(pht)(bpy)(H₂O)]·3H₂O}_n (pht is phthalate and bpy is 4,4′-bipyridine) and the role of solvent water clusters in structure stability

M. A. Harvey, S. Suarez, F. Doctorovich, F. D. Cukiernik and R. Baggio

The Co^II cation in poly[[aqua(μ-benzene-1,2-dicarboxylato-κ³O¹,O²:O¹)(μ-4,4′-bipyridine-κ²N:N′)cobalt(II)] trihydrate], {[Co(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]·3H₂O}_n, is octahedrally coordinated by two N atoms of two 4,4′-bipyridine ligands, three O atoms from phthalate anions and a fourth O atom from a coordinated water molecule. The packing consists of planes of coordination polymers linked by hydrogen bonds mediated by three solvent water molecules; the linkage is achieved by the water molecules forming intricate oligomeric clusters which also involve the O atoms of the phthalate ligands.

Keywords: crystal structure; hydrated cobalt complex; two-dimensional covalent arrays; two-dimensional coordination polymer; stabilizing water clusters; TBG porous coordination polymer.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614006950/yf3058sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229614006950/yf3058Isup2.hkl Contains datablock I

CCDC reference: 994191

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Poly[[aqua(µ-benzene-1,2-dicarboxylato-κ³O¹,O²:O¹)(µ-4,4'-bipyridine-κ²N:N')cobalt(II)] trihydrate] top

Crystal data top

[Co(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]·3H₂O	F(000) = 466
M_r = 451.30	D_x = 1.566 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3445 reflections
a = 11.0975 (6) Å	θ = 3.8–27.9°
b = 8.4039 (3) Å	µ = 0.95 mm⁻¹
c = 11.3732 (6) Å	T = 294 K
β = 115.564 (7)°	Prism, red
V = 956.85 (10) Å³	0.35 × 0.30 × 0.25 mm
Z = 2

Data collection top

Oxford Gemini S Ultra CCD area-detector diffractometer	4451 independent reflections
Radiation source: fine-focus sealed tube	4096 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω scans, thick slices	θ_max = 28.9°, θ_min = 3.6°
Absorption correction: multi-scan (CrysAlisPro; Oxford Diffraction, 2009)	h = −15→15
T_min = 0.72, T_max = 0.74	k = −11→11
14398 measured reflections	l = −14→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0448P)² + 0.4467P] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max = 0.006
4451 reflections	Δρ_max = 0.56 e Å⁻³
286 parameters	Δρ_min = −0.31 e Å⁻³
17 restraints	Absolute structure: Flack (1983), with 2206 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.016 (12)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.35427 (3)	0.50053 (6)	0.41073 (2)	0.02221 (7)
O11	0.0305 (2)	0.2427 (3)	0.2280 (2)	0.0559 (6)
O21	0.15083 (17)	0.4560 (2)	0.32261 (18)	0.0326 (4)
O31	0.39059 (19)	0.2551 (2)	0.42902 (16)	0.0292 (4)
O41	0.44053 (15)	0.0217 (2)	0.52815 (15)	0.0281 (4)
C11	0.1390 (2)	0.2443 (3)	0.4571 (2)	0.0288 (5)
C21	0.0448 (3)	0.2621 (3)	0.5065 (3)	0.0397 (6)
H21	−0.0332	0.3187	0.4587	0.048*
C31	0.0648 (3)	0.1978 (4)	0.6243 (3)	0.0484 (8)
H31	0.0012	0.2125	0.6561	0.058*
C41	0.1780 (3)	0.1122 (4)	0.6954 (3)	0.0481 (8)
H41	0.1920	0.0696	0.7757	0.058*
C51	0.2719 (3)	0.0893 (4)	0.6464 (3)	0.0399 (6)
H51	0.3469	0.0271	0.6927	0.048*
C61	0.2552 (2)	0.1586 (3)	0.5287 (2)	0.0277 (5)
C71	0.1063 (2)	0.3192 (3)	0.3255 (3)	0.0319 (5)
C81	0.3688 (2)	0.1452 (3)	0.4906 (2)	0.0232 (5)
N12	0.37286 (17)	0.5158 (3)	0.60643 (16)	0.0253 (4)
N22	0.34412 (18)	0.4913 (4)	1.21618 (16)	0.0295 (4)
C12	0.2668 (3)	0.5679 (4)	0.6219 (2)	0.0340 (6)
H12	0.1949	0.6083	0.5493	0.041*
C22	0.2578 (3)	0.5651 (3)	0.7385 (2)	0.0347 (6)
H22	0.1814	0.6027	0.7437	0.042*
C32	0.3635 (2)	0.5059 (4)	0.84854 (19)	0.0268 (4)
C42	0.4757 (3)	0.4573 (3)	0.8339 (2)	0.0346 (6)
H42	0.5505	0.4203	0.9054	0.041*
C52	0.4761 (2)	0.4637 (3)	0.7132 (2)	0.0318 (6)
H52	0.5523	0.4300	0.7057	0.038*
C62	0.2767 (3)	0.5978 (4)	1.1257 (2)	0.0403 (7)
H62	0.2239	0.6707	1.1438	0.048*
C72	0.2803 (3)	0.6066 (4)	1.0062 (3)	0.0414 (7)
H72	0.2326	0.6852	0.9468	0.050*
C82	0.3556 (2)	0.4975 (4)	0.97543 (19)	0.0280 (4)
C92	0.4228 (3)	0.3828 (3)	1.0675 (2)	0.0369 (6)
H92	0.4732	0.3057	1.0503	0.044*
C102	0.4148 (3)	0.3834 (3)	1.1853 (2)	0.0367 (6)
H102	0.4607	0.3053	1.2462	0.044*
O1W	0.30884 (19)	0.74617 (19)	0.39430 (17)	0.0359 (4)
H1WA	0.3694 (9)	0.8086 (14)	0.4445 (19)	0.043*
H1WB	0.2452 (8)	0.8072 (13)	0.3472 (15)	0.043*
O2W	0.1079 (2)	0.9216 (3)	0.2094 (3)	0.0914 (10)
H2WA	0.1460 (8)	0.947 (2)	0.1613 (9)	0.110*
H2WB	0.0868 (16)	1.0100 (13)	0.232 (2)	0.110*
O3W	0.1274 (5)	0.9518 (4)	−0.0226 (3)	0.132 (2)	0.80
H3WA	0.0890 (15)	0.8997 (18)	−0.0931 (9)	0.159*	0.80
H3WB	0.093 (2)	1.0440 (12)	−0.041 (3)	0.159*	0.80
O4W	−0.0925 (4)	0.7527 (6)	0.0073 (3)	0.124 (2)	0.70
H4WB	−0.0722 (18)	0.788 (4)	−0.0518 (11)	0.149*	0.70
H4WA	−0.0434 (19)	0.8035 (15)	0.0761 (8)	0.149*	0.70

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02774 (13)	0.02391 (12)	0.01810 (12)	0.00001 (15)	0.01284 (10)	0.00015 (14)
O11	0.0597 (14)	0.0495 (12)	0.0385 (11)	−0.0157 (11)	0.0023 (11)	−0.0059 (10)
O21	0.0305 (8)	0.0311 (10)	0.0351 (9)	−0.0013 (7)	0.0130 (8)	0.0044 (6)
O31	0.0391 (9)	0.0255 (8)	0.0319 (9)	0.0032 (8)	0.0236 (8)	0.0034 (7)
O41	0.0297 (7)	0.0250 (9)	0.0317 (8)	0.0021 (7)	0.0153 (6)	0.0043 (7)
C11	0.0273 (11)	0.0261 (11)	0.0356 (12)	−0.0056 (9)	0.0159 (10)	−0.0039 (10)
C21	0.0295 (12)	0.0413 (14)	0.0528 (16)	−0.0012 (12)	0.0221 (13)	−0.0015 (13)
C31	0.0427 (15)	0.0610 (19)	0.0571 (18)	−0.0113 (14)	0.0364 (15)	−0.0095 (15)
C41	0.0511 (17)	0.0612 (19)	0.0448 (16)	−0.0056 (15)	0.0329 (14)	0.0074 (14)
C51	0.0411 (15)	0.0473 (15)	0.0379 (14)	0.0019 (13)	0.0233 (13)	0.0106 (12)
C61	0.0290 (11)	0.0268 (11)	0.0322 (12)	−0.0012 (9)	0.0178 (10)	−0.0006 (9)
C71	0.0257 (11)	0.0353 (13)	0.0351 (13)	0.0016 (10)	0.0135 (11)	−0.0008 (10)
C81	0.0243 (11)	0.0265 (11)	0.0198 (10)	−0.0033 (9)	0.0104 (9)	−0.0034 (8)
N12	0.0290 (8)	0.0289 (10)	0.0210 (8)	0.0021 (10)	0.0136 (7)	−0.0019 (9)
N22	0.0337 (9)	0.0376 (10)	0.0211 (8)	0.0003 (12)	0.0156 (7)	0.0027 (11)
C12	0.0347 (13)	0.0477 (14)	0.0209 (11)	0.0086 (11)	0.0132 (10)	0.0017 (10)
C22	0.0337 (13)	0.0502 (14)	0.0256 (12)	0.0070 (11)	0.0178 (11)	−0.0002 (10)
C32	0.0355 (10)	0.0289 (10)	0.0208 (9)	0.0012 (14)	0.0166 (8)	−0.0024 (14)
C42	0.0340 (12)	0.0468 (17)	0.0225 (11)	0.0113 (10)	0.0118 (10)	0.0051 (9)
C52	0.0322 (11)	0.0406 (16)	0.0275 (11)	0.0086 (10)	0.0176 (10)	0.0014 (9)
C62	0.0553 (17)	0.0465 (15)	0.0269 (13)	0.0215 (13)	0.0250 (13)	0.0056 (11)
C72	0.0567 (17)	0.0472 (15)	0.0243 (12)	0.0206 (13)	0.0212 (12)	0.0089 (11)
C82	0.0331 (10)	0.0340 (10)	0.0195 (9)	0.0039 (15)	0.0136 (8)	0.0007 (14)
C92	0.0516 (16)	0.0389 (13)	0.0276 (12)	0.0141 (12)	0.0241 (12)	0.0033 (10)
C102	0.0526 (16)	0.0367 (13)	0.0251 (12)	0.0102 (13)	0.0209 (12)	0.0054 (10)
O1W	0.0405 (10)	0.0263 (9)	0.0335 (10)	−0.0014 (9)	0.0089 (8)	−0.0038 (7)
O2W	0.100 (2)	0.0791 (19)	0.0711 (19)	0.0338 (18)	0.0147 (17)	−0.0068 (15)
O3W	0.177 (5)	0.141 (6)	0.071 (3)	0.019 (4)	0.047 (3)	−0.025 (3)
O4W	0.138 (5)	0.124 (5)	0.084 (3)	0.012 (4)	0.024 (3)	−0.012 (3)

Geometric parameters (Å, º) top

Co1—O21	2.0710 (18)	N22—Co1^iv	2.1678 (17)
Co1—O41ⁱ	2.0819 (16)	C12—C22	1.373 (3)
Co1—O31	2.0947 (18)	C12—H12	0.9300
Co1—O1W	2.1141 (17)	C22—C32	1.387 (3)
Co1—N12	2.1486 (17)	C22—H22	0.9300
Co1—N22ⁱⁱ	2.1678 (17)	C32—C42	1.387 (3)
O11—C71	1.244 (3)	C32—C82	1.485 (3)
O21—C71	1.257 (3)	C42—C52	1.375 (3)
O31—C81	1.244 (3)	C42—H42	0.9300
O41—C81	1.265 (3)	C52—H52	0.9300
O41—Co1ⁱⁱⁱ	2.0819 (16)	C62—C72	1.380 (4)
C11—C21	1.392 (4)	C62—H62	0.9300
C11—C61	1.392 (3)	C72—C82	1.383 (4)
C11—C71	1.516 (4)	C72—H72	0.9300
C21—C31	1.371 (4)	C82—C92	1.381 (4)
C21—H21	0.9300	C92—C102	1.380 (3)
C31—C41	1.368 (5)	C92—H92	0.9300
C31—H31	0.9300	C102—H102	0.9300
C41—C51	1.391 (4)	O1W—H1WA	0.8501 (10)
C41—H41	0.9300	O1W—H1WB	0.8501 (10)
C51—C61	1.396 (3)	O2W—H2WA	0.8501 (10)
C51—H51	0.9300	O2W—H2WB	0.8500 (10)
C61—C81	1.504 (3)	O3W—H3WA	0.8500 (10)
N12—C52	1.333 (3)	O3W—H3WB	0.8503 (10)
N12—C12	1.336 (3)	O4W—H4WB	0.8500 (10)
N22—C62	1.325 (4)	O4W—H4WA	0.8501 (10)
N22—C102	1.341 (4)

O21—Co1—O41ⁱ	169.71 (7)	C52—N12—C12	116.54 (19)
O21—Co1—O31	89.59 (7)	C52—N12—Co1	125.78 (15)
O41ⁱ—Co1—O31	85.12 (7)	C12—N12—Co1	117.34 (15)
O21—Co1—O1W	88.01 (7)	C62—N22—C102	116.84 (19)
O41ⁱ—Co1—O1W	97.52 (7)	C62—N22—Co1^iv	122.12 (19)
O31—Co1—O1W	177.00 (8)	C102—N22—Co1^iv	120.85 (17)
O21—Co1—N12	96.29 (7)	N12—C12—C22	123.9 (2)
O41ⁱ—Co1—N12	92.68 (6)	N12—C12—H12	118.1
O31—Co1—N12	91.59 (8)	C22—C12—H12	118.1
O1W—Co1—N12	86.89 (8)	C12—C22—C32	119.4 (2)
O21—Co1—N22ⁱⁱ	86.21 (7)	C12—C22—H22	120.3
O41ⁱ—Co1—N22ⁱⁱ	84.92 (7)	C32—C22—H22	120.3
O31—Co1—N22ⁱⁱ	89.38 (9)	C22—C32—C42	116.8 (2)
O1W—Co1—N22ⁱⁱ	92.25 (9)	C22—C32—C82	120.8 (2)
N12—Co1—N22ⁱⁱ	177.33 (9)	C42—C32—C82	122.4 (2)
C71—O21—Co1	120.77 (16)	C52—C42—C32	119.9 (2)
C81—O31—Co1	135.33 (16)	C52—C42—H42	120.1
C81—O41—Co1ⁱⁱⁱ	128.39 (15)	C32—C42—H42	120.1
C21—C11—C61	119.1 (2)	N12—C52—C42	123.4 (2)
C21—C11—C71	116.8 (2)	N12—C52—H52	118.3
C61—C11—C71	124.0 (2)	C42—C52—H52	118.3
C31—C21—C11	121.2 (3)	N22—C62—C72	123.7 (2)
C31—C21—H21	119.4	N22—C62—H62	118.2
C11—C21—H21	119.4	C72—C62—H62	118.2
C41—C31—C21	120.3 (3)	C62—C72—C82	119.4 (2)
C41—C31—H31	119.8	C62—C72—H72	120.3
C21—C31—H31	119.8	C82—C72—H72	120.3
C31—C41—C51	119.5 (3)	C92—C82—C72	117.3 (2)
C31—C41—H41	120.3	C92—C82—C32	122.1 (2)
C51—C41—H41	120.3	C72—C82—C32	120.6 (2)
C41—C51—C61	120.9 (3)	C102—C92—C82	119.6 (2)
C41—C51—H51	119.6	C102—C92—H92	120.2
C61—C51—H51	119.6	C82—C92—H92	120.2
C11—C61—C51	118.9 (2)	N22—C102—C92	123.1 (2)
C11—C61—C81	123.4 (2)	N22—C102—H102	118.4
C51—C61—C81	117.6 (2)	C92—C102—H102	118.4
O11—C71—O21	124.8 (3)	Co1—O1W—H1WA	117.0 (9)
O11—C71—C11	116.6 (2)	Co1—O1W—H1WB	138.3 (10)
O21—C71—C11	118.4 (2)	H1WA—O1W—H1WB	104.6 (9)
O31—C81—O41	123.5 (2)	H2WA—O2W—H2WB	104.6 (11)
O31—C81—C61	119.8 (2)	H3WA—O3W—H3WB	104.3 (11)
O41—C81—C61	116.6 (2)	H4WB—O4W—H4WA	105.5 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O41^v	0.85 (2)	2.02 (1)	2.810 (2)	154 (1)
O1W—H1WB···O2W	0.85 (1)	1.91 (1)	2.743 (3)	167 (1)
O2W—H2WA···O3W	0.85 (1)	2.01 (1)	2.751 (5)	145 (1)
O2W—H2WB···O11^v	0.85 (1)	2.05 (1)	2.867 (4)	161 (2)
O3W—H3WA···O11^vi	0.85 (1)	2.02 (1)	2.843 (4)	162 (2)
O3W—H3WB···O4W^vi	0.85 (2)	1.80 (1)	2.576 (6)	152 (2)
O4W—H4WB···O11^vi	0.85 (2)	2.28 (2)	3.038 (4)	150 (2)
O4W—H4WA···O2W	0.85 (1)	1.98 (1)	2.799 (5)	162 (2)

Symmetry codes: (v) x, y+1, z; (vi) −x, y+1/2, −z.

Summary of transition metal complexes of general formula Tr(pht)_n₁(bpy)_n₂(H₂O)_n3.(H₂O)_n4, represented by the shorthand notation n1:n2:n3:(n4) top

CSD refcode	Tr	Space group	a (Å)	b (Å)	c (Å)	α (°)	β (°)	γ (°)	V (Å³)	ρ (g cm^-1)
Group A, formula 1:1:2:(2)
BASMIS01	Mn	P2/n	7.69	11.59	10.75	90	92.67	90	957.16	1.552
JEKTUP	Zn	P2/n	7.63	11.32	10.81	90	92.44	90	933.35	1.629
NEDXEZ	Cd	P2/n	7.79	11.65	10.70	90	92.59	90	969.73	1.729
NEDXOJ01	Co	P2/n	7.61	11.36	10.81	90	92.28	90	933.65	1.605
QEHCUC	Fe	P2/n	7.65	11.39	10.79	90	92.67	90	939.15	1.585
TEJKUP*	Cu	P2/c	7.70	11.10	12.97	90	123.7	90	922.25	1.642
WIPFOR*	Ni	P2/c	7.62	11.37	12.95	90	123.6	90	934.16	1.604

Group B, formula 2:1:0:(0)
FEQSOK	Cd	I4₁22	8.29	8.29	33.75	90	90	90	2321.90	1.713
LESBEQ	Co	I4122	8.16	8.16	32.93	90	90	90	2190.30	1.654

Group C, formula 2:2:0:(0)
IZASIL	Zn	P1	7.51	10	22.08	84.31	88.08	71.02	1560.50	1.507

Group D, formula 1:1:2:(0.5)
WEDNEA	Ni	P4₁2₁2	11.30	11.27	29.90	90	90	90	3796.60	1.484

Group E, formula 1:1:1:(3)
KAGQEP	Ni	P2₁	11.10	8.38	11.27	90	115.4	90	949.42	1.578
(I)	Co		11.10	8.40	11.37	90	115.6	90	956.85	1.566

(*): In spite of being refined in space group P2/c, these structures are isomorphous with those described in P2/n.

π–π contacts (Å, °) top

Cg···Cg'	CCD (Å)	IPD (Å)	DA (°)
Cg1···Cg2	3.5839 (19)	3.48 (5)	16.42 (16)

Cg1 is the centroid of the C11/C21/C31/C41/C51/C61 ring and Cg2 that of the N12/C12/C22/C32/C42/C52 ring.

IPD is the interplanar distance, CCD the centre-to-centre distance and DA the dihedral angle between planes; for details, see Janiak (2000).

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The structure of {[Co(pht)(bpy)(H2O)]·3H2O}n (pht is phthalate and bpy is 4,4′-bi­pyridine) and the role of solvent water clusters in structure stability

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The structure of {[Co(pht)(bpy)(H₂O)]·3H₂O}_n (pht is phthalate and bpy is 4,4′-bipyridine) and the role of solvent water clusters in structure stability