Salts of aromatic carboxylates: the crystal structures of nickel(II) and cobalt(II) 2,6-naphthalenedicarboxylate tetrahydrate

The crystal structures of isostructural 2,6-naphthalenedicarboxylate tetrahydrate salts of nickel(II) and cobalt(II) have been determined using Monte Carlo simulated annealing techniques and laboratory X-ray powder diffraction data. These compounds crystallize in the triclinic space group P, with Z = 2; a = 10.0851 (4), b = 10.9429 (5), c = 6.2639 (3) Å, α = 98.989 (2), β = 87.428 (3), γ = 108.015 (2)°, V = 649.32 (5) ų for [Ni(C₁₂H₆O₄)(H₂O)₄], and a = 10.1855 (6), b = 10.8921 (6), c = 6.2908 (5) Å, α = 98.519 (4), β = 87.563 (4), γ = 108.304 (3)°, V = 655.28 (8) ų for [Co(C₁₂H₆O₄)(H₂O)₄]. The water-molecule H atoms were located by quantum chemical geometry optimization using CASTEP. The structure consists of alternating hydrocarbon and metal/oxygen layers parallel to the ac plane. Each naphthalenedicarboxylate anion bridges two metal cations; each carboxyl group is monodentate. The resulting structure contains infinite chains parallel to [111]. The octahedral coordination sphere of the metal cations contains trans carboxylates and four equatorial water molecules. The carboxyl groups are rotated by 15–20° out of the naphthalene plane. The metal/oxygen layers are characterized by an extensive hydrogen-bonding network. The orientations of the carboxyl groups are determined by the formation of short (O...O = 2.53 Å) hydrogen bonds between the carbonyl O atoms and the cis water molecules. Molecular mechanics energy minimizations suggest that coordination and hydrogen-bonding interactions are most important in determining the crystal packing.

Computing details

For both compounds, program(s) used to refine structure: GSAS.

(KADU445)

Crystal data

Triclinic, P1	α = 98.987 (2)°
a = 10.0848 (4) Å	β = 87.427 (3)°
b = 10.9428 (5) Å	γ = 108.0158 (18)°
c = 6.2639 (3) Å	KG1, KG2 radiation

Data collection

2θmin = 13.043°, 2θmax = 89.983°, 2θstep = 0.02°

Refinement

Rp = 0.049	3848 data points
Rwp = 0.065	52 parameters
Rexp = 0.022	30 restraints

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

	x	y	z	Uiso*/Ueq
C1	0.3539 (10)	1.1253 (7)	0.7132 (10)	0.031 (2)*
C2	0.4652 (9)	1.1749 (7)	0.5782 (11)	0.031 (2)*
C3	0.4631 (9)	1.1189 (8)	0.3616 (11)	0.031 (2)*
C4	0.3497 (10)	1.0133 (8)	0.2805 (9)	0.031 (2)*
C5	0.1241 (10)	0.8574 (7)	0.3347 (10)	0.031 (2)*
C6	0.0128 (10)	0.8077 (7)	0.4697 (13)	0.031 (2)*
C7	0.0148 (10)	0.8638 (7)	0.6862 (12)	0.031 (2)*
C8	0.1282 (10)	0.9694 (7)	0.7673 (10)	0.031 (2)*
C9	0.2400 (9)	1.0195 (7)	0.6326 (9)	0.031 (2)*
C10	0.2379 (9)	0.9632 (7)	0.4153 (9)	0.031 (2)*
H1	0.3568 (11)	1.1698 (8)	0.8812 (11)	0.05*
H3	0.5496 (10)	1.1574 (9)	0.2565 (13)	0.05*
H4	0.3495 (11)	0.9707 (9)	0.1119 (9)	0.05*
H5	0.1211 (11)	0.8129 (9)	0.1667 (11)	0.05*
H7	−0.0716 (10)	0.8253 (8)	0.7914 (14)	0.05*
H8	0.1284 (11)	1.0120 (9)	0.9360 (11)	0.05*
C11	0.5877 (10)	1.2891 (8)	0.6662 (14)	0.022 (2)*
C12	−0.1097 (10)	0.6936 (8)	0.3817 (16)	0.022 (2)*
O1	0.5949 (12)	1.3121 (12)	0.868 (2)	0.022 (2)*
O2	0.6826 (15)	1.3411 (12)	0.5260 (19)	0.022 (2)*
O3	−0.2203 (17)	0.6798 (13)	0.4952 (18)	0.022 (2)*
O4	−0.0989 (15)	0.6339 (12)	0.214 (3)	0.022 (2)*
Ni	0.7479 (6)	1.4790 (5)	1.0272 (9)	0.0357 (17)*
O5	0.8846 (15)	1.4778 (14)	0.760 (2)	0.028 (3)*
O6	0.6051 (15)	1.4822 (12)	1.278 (2)	0.028 (3)*
O7	0.8289 (13)	1.3466 (11)	1.145 (2)	0.028 (3)*
O8	0.6873 (16)	1.6231 (11)	0.898 (2)	0.028 (3)*
H5a	0.86528	1.38675	0.74713	0.03*
H5b	0.97172	1.50115	0.85866	0.03*
H6a	0.53731	1.39076	1.26716	0.03*
H6b	0.55396	1.54789	1.2619	0.03*
H7a	0.84631	1.38881	1.30045	0.03*
H7b	0.74702	1.27221	1.15524	0.03*
H8a	0.67419	1.57228	0.75349	0.03*
H8b	0.58858	1.59919	0.9664	0.03*

(KADU440)

Crystal data

Triclinic, P1	α = 98.522 (4)°
a = 10.1856 (6) Å	β = 87.573 (4)°
b = 10.8931 (6) Å	γ = 108.300 (3)°
c = 6.2902 (5) Å	KG1, KG2 radiation

Data collection

2θmin = 13.043°, 2θmax = 89.983°, 2θstep = 0.02°

Refinement

Rp = 0.030	3848 data points
Rwp = 0.040	52 parameters
Rexp = 0.026	30 restraints

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

	x	y	z	Uiso*/Ueq
C1	0.3455 (19)	1.1260 (15)	0.708 (2)	0.041 (4)*
C2	0.4611 (18)	1.1748 (15)	0.581 (2)	0.041 (4)*
C3	0.4669 (19)	1.1159 (15)	0.370 (2)	0.041 (4)*
C4	0.357 (2)	1.0084 (15)	0.2846 (18)	0.041 (4)*
C5	0.131 (2)	0.8515 (14)	0.326 (2)	0.041 (4)*
C6	0.015 (2)	0.8027 (13)	0.452 (2)	0.041 (4)*
C7	0.0092 (19)	0.8615 (14)	0.664 (3)	0.041 (4)*
C8	0.1191 (19)	0.9690 (15)	0.749 (2)	0.041 (4)*
C9	0.2352 (19)	1.0183 (14)	0.6229 (19)	0.041 (4)*
C10	0.241 (2)	0.9592 (13)	0.4105 (18)	0.041 (4)*
H1	0.342 (2)	1.1727 (18)	0.872 (2)	0.05*
H3	0.557 (2)	1.1538 (16)	0.272 (2)	0.05*
H4	0.363 (2)	0.9637 (17)	0.1198 (19)	0.05*
H5	0.134 (2)	0.8048 (16)	0.162 (2)	0.05*
H7	−0.081 (2)	0.8237 (15)	0.762 (3)	0.05*
H8	0.113 (2)	1.0138 (18)	0.914 (2)	0.05*
C11	0.5798 (19)	1.2910 (17)	0.674 (3)	0.003 (4)*
C12	−0.104 (2)	0.6865 (14)	0.360 (3)	0.003 (4)*
O1	0.587 (2)	1.315 (3)	0.864 (4)	0.003 (4)*
O2	0.679 (2)	1.333 (2)	0.535 (4)	0.003 (4)*
O3	−0.227 (3)	0.687 (2)	0.491 (4)	0.003 (4)*
O4	−0.101 (3)	0.635 (3)	0.207 (4)	0.003 (4)*
Co	0.7467 (12)	1.4819 (11)	1.0291 (19)	0.052 (4)*
O5	0.883 (3)	1.466 (3)	0.746 (4)	0.023 (5)*
O6	0.602 (3)	1.490 (2)	1.272 (4)	0.023 (5)*
O7	0.827 (2)	1.348 (2)	1.137 (4)	0.023 (5)*
O8	0.694 (3)	1.623 (2)	0.902 (4)	0.023 (5)*
H5a	0.86416	1.38101	0.75995	0.03*
H5b	0.96329	1.50775	0.86141	0.03*
H6a	0.54693	1.39876	1.25994	0.03*
H6b	0.66144	1.49091	1.39108	0.03*
H7a	0.84693	1.37086	1.28164	0.03*
H7b	0.75374	1.26519	1.11385	0.03*
H8a	0.66284	1.56483	0.7441	0.03*
H8b	0.59358	1.59916	0.96558	0.03*