Intra- and supra-molecular inter-actions in cis,mer-diaqua-tris-(1H-imidazole-κN(3))(terephthalato-κO)cobalt(II) monohydrate.

In the title compound, [Co(C(8)H(4)O(4))(C(3)H(4)N(2))(3)(H(2)O)(2)]·H(2)O, the cisoid angles are in the range 85.59 (5)-93.56 (5)°, while two equal transoid angles deviate significantly from the ideal linear angle, the third being almost linear. One carboxyl-ate group is almost coplanar [1.23 (13)°] with the plane of its parent aromatic ring, although it has one O-atom donor involved in one coordination and one hydrogen bond as acceptor. The other carboxyl-ate group does not coordinate and is rotated out of this plane with a torsional twist of 17.27 (20)°. The coordination neutral entity, based on aqua ligands and two cyclic co-ligands seems, at first sight, monomeric. Strongly tight, via one intra-molecular hydrogen bond between aqua and carboxyl-ate O atoms, it brings out a quasi-planar six-membered ring around the Co(II) atom, turning the CoN(3)O(3) coordination octa-hedron into a new building block. The rigidity of this feature associated with several hydrogen-bonded arrays yields an extended structure. In the resulting supra-molecular packing, a binuclear hydrated Co(II) assembly, built up from triple strands driven by different heterosynthons, embodies the synergy of coordination, covalent and hydrogen bonds.

Related literature

For general background to important structural features inducing some inter­esting properties, see: Chen et al. (1996 ▶); Yang et al. (2002 ▶); Ye & Chen (2003 ▶); Xie et al. (2009 ▶); Baca et al. (2003 ▶). For related compounds or structures, see: Niu et al. (2004 ▶); Tong et al. (2002 ▶); Liu et al. (2001 ▶, 2003 ▶); Zeng et al. (1997 ▶).

Experimental

Crystal data

[Co(C8H4O4)(C3H4N2)3(H2O)2]·H2O

M = 481.34

Monoclinic,

a = 7.65363 (8) Å

b = 10.45169 (13) Å

c = 24.7538 (3) Å

β = 90.227 (1)°

V = 1980.12 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.92 mm−1

T = 291 K

0.21 × 0.14 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009 ▶), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 ▶)] T min = 0.871, T max = 0.935

86135 measured reflections

4760 independent reflections

4153 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.071

S = 1.08

4760 reflections

316 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812011993/ds2181sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011993/ds2181Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co(C8H4O4)(C3H4N2)3(H2O)2]·H2O	F(000) = 996
Mr = 481.34	Dx = 1.615 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 35056 reflections
a = 7.65363 (8) Å	θ = 3.3–32.9°
b = 10.45169 (13) Å	µ = 0.92 mm−1
c = 24.7538 (3) Å	T = 291 K
β = 90.227 (1)°	Prism, pink
V = 1980.12 (4) Å3	0.21 × 0.14 × 0.08 mm
Z = 4

Oxford Diffraction Xcalibur diffractometer	4760 independent reflections
Radiation source: fine-focus sealed tube	4153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
Detector resolution: 10.4508 pixels mm-1	θmax = 28.0°, θmin = 3.4°
wσcans	h = −10→10
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −13→13
Tmin = 0.871, Tmax = 0.935	l = −32→32
86135 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0265P)2 + 1.5429P] where P = (Fo2 + 2Fc2)/3
4760 reflections	(Δ/σ)max = 0.003
316 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction (2009) Analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995).

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. CrysAlis RED, Oxford Diffraction Ltd 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.

	x	y	z	Uiso*/Ueq
Co	0.44254 (2)	0.144772 (19)	0.652633 (8)	0.00874 (6)
O1W	0.52240 (15)	0.33528 (11)	0.67705 (4)	0.0123 (2)
O2W	0.60355 (16)	0.07515 (12)	0.71527 (5)	0.0147 (2)
O3W	0.66608 (15)	0.36561 (12)	0.78325 (5)	0.0149 (2)
O1	0.29257 (14)	0.22971 (10)	0.58868 (4)	0.0115 (2)
O2	0.31457 (15)	0.43979 (11)	0.60544 (4)	0.0165 (2)
O3	0.05014 (14)	0.36582 (10)	0.32226 (4)	0.0130 (2)
O4	0.16128 (14)	0.56111 (11)	0.33113 (4)	0.0134 (2)
C1	0.28701 (19)	0.34725 (15)	0.57476 (6)	0.0116 (3)
C2	0.24336 (19)	0.37422 (15)	0.51627 (6)	0.0115 (3)
C3	0.21121 (19)	0.27458 (15)	0.48037 (6)	0.0115 (3)
H3	0.2188	0.1885	0.4925	0.014*
C4	0.16812 (19)	0.30000 (15)	0.42695 (6)	0.0117 (3)
H4	0.1412	0.2315	0.4031	0.014*
C5	0.16416 (19)	0.42578 (15)	0.40819 (6)	0.0106 (3)
C6	0.2013 (2)	0.52539 (15)	0.44372 (6)	0.0154 (3)
H6	0.2019	0.6111	0.4310	0.018*
C7	0.2375 (2)	0.49999 (16)	0.49776 (6)	0.0160 (3)
H7	0.2584	0.5686	0.5221	0.019*
C8	0.12281 (19)	0.45417 (14)	0.34977 (6)	0.0101 (3)
N1	0.66337 (16)	0.13362 (12)	0.60043 (5)	0.0113 (3)
N2	0.93656 (18)	0.13617 (13)	0.57266 (6)	0.0143 (3)
C9	0.8290 (2)	0.13727 (15)	0.61550 (6)	0.0128 (3)
H9	0.8674	0.1403	0.6520	0.015*
C10	0.8336 (2)	0.13227 (16)	0.52700 (6)	0.0155 (3)
H10	0.8722	0.1310	0.4906	0.019*
C11	0.6653 (2)	0.13062 (15)	0.54460 (6)	0.0143 (3)
H11	0.5647	0.1278	0.5220	0.017*
N3	0.23535 (16)	0.16873 (12)	0.70755 (5)	0.0115 (3)
N4	−0.00080 (18)	0.25190 (14)	0.74341 (5)	0.0145 (3)
C12	0.1779 (2)	0.09015 (16)	0.74877 (6)	0.0146 (3)
H12	0.2327	0.0129	0.7599	0.017*
C13	0.0312 (2)	0.14045 (16)	0.77079 (6)	0.0152 (3)
H13	−0.0359	0.1054	0.7994	0.018*
C14	0.12406 (19)	0.26542 (15)	0.70594 (6)	0.0127 (3)
H14	0.1315	0.3352	0.6815	0.015*
N5	0.36196 (16)	−0.04089 (12)	0.62981 (5)	0.0120 (3)
N6	0.23014 (18)	−0.22776 (14)	0.63208 (6)	0.0157 (3)
C15	0.4649 (2)	−0.13139 (15)	0.60470 (6)	0.0141 (3)
H15	0.5754	−0.1150	0.5888	0.017*
C16	0.3850 (2)	−0.24738 (16)	0.60607 (6)	0.0159 (3)
H16	0.4278	−0.3258	0.5919	0.019*
C17	0.2212 (2)	−0.10428 (16)	0.64582 (6)	0.0147 (3)
H17	0.1262	−0.0667	0.6647	0.018*
H2N	1.048 (3)	0.147 (2)	0.5743 (9)	0.030 (6)*
H4N	−0.088 (3)	0.301 (2)	0.7480 (8)	0.022 (5)*
H6N	0.156 (3)	−0.283 (2)	0.6416 (9)	0.026 (6)*
H1W	0.454 (3)	0.381 (3)	0.6584 (10)	0.043 (7)*
H2W	0.623 (3)	0.360 (2)	0.6673 (9)	0.034 (6)*
H3W	0.576 (3)	0.085 (2)	0.7469 (10)	0.036 (7)*
H4W	0.670 (3)	0.014 (2)	0.7123 (9)	0.029 (6)*
H5W	0.610 (3)	0.365 (2)	0.7556 (9)	0.025 (6)*
H6W	0.639 (3)	0.301 (2)	0.7995 (9)	0.031 (6)*

	U11	U22	U33	U12	U13	U23
Co	0.00883 (10)	0.00915 (11)	0.00823 (10)	−0.00041 (7)	0.00022 (7)	0.00042 (7)
O1W	0.0120 (5)	0.0125 (6)	0.0125 (5)	−0.0014 (4)	−0.0014 (4)	0.0007 (4)
O2W	0.0183 (6)	0.0166 (6)	0.0093 (5)	0.0060 (5)	−0.0001 (4)	0.0001 (4)
O3W	0.0167 (6)	0.0158 (6)	0.0120 (5)	−0.0031 (5)	−0.0020 (5)	0.0025 (5)
O1	0.0127 (5)	0.0111 (5)	0.0107 (5)	−0.0006 (4)	−0.0015 (4)	0.0024 (4)
O2	0.0244 (6)	0.0126 (5)	0.0125 (5)	−0.0002 (5)	−0.0050 (5)	−0.0009 (4)
O3	0.0158 (5)	0.0130 (5)	0.0101 (5)	−0.0024 (4)	−0.0015 (4)	−0.0003 (4)
O4	0.0146 (5)	0.0124 (5)	0.0134 (5)	−0.0022 (4)	−0.0017 (4)	0.0038 (4)
C1	0.0094 (6)	0.0142 (7)	0.0113 (7)	−0.0001 (6)	0.0001 (5)	0.0019 (6)
C2	0.0114 (7)	0.0137 (7)	0.0093 (7)	0.0006 (6)	−0.0007 (5)	0.0011 (6)
C3	0.0116 (7)	0.0103 (7)	0.0127 (7)	0.0001 (5)	−0.0008 (6)	0.0022 (6)
C4	0.0113 (7)	0.0116 (7)	0.0121 (7)	0.0003 (6)	0.0005 (5)	−0.0013 (6)
C5	0.0095 (6)	0.0125 (7)	0.0098 (7)	−0.0001 (5)	0.0000 (5)	0.0006 (6)
C6	0.0218 (8)	0.0101 (7)	0.0141 (7)	−0.0013 (6)	−0.0020 (6)	0.0015 (6)
C7	0.0230 (8)	0.0117 (8)	0.0131 (7)	−0.0015 (6)	−0.0037 (6)	−0.0015 (6)
C8	0.0079 (6)	0.0130 (7)	0.0095 (7)	0.0012 (5)	0.0011 (5)	−0.0006 (6)
N1	0.0120 (6)	0.0118 (6)	0.0101 (6)	−0.0012 (5)	0.0007 (5)	−0.0010 (5)
N2	0.0108 (6)	0.0168 (7)	0.0153 (7)	−0.0009 (5)	0.0021 (5)	0.0002 (5)
C9	0.0120 (7)	0.0138 (7)	0.0126 (7)	−0.0012 (6)	0.0009 (6)	0.0000 (6)
C10	0.0157 (7)	0.0194 (8)	0.0114 (7)	−0.0020 (6)	0.0029 (6)	−0.0007 (6)
C11	0.0153 (7)	0.0173 (8)	0.0105 (7)	−0.0021 (6)	0.0004 (6)	0.0002 (6)
N3	0.0116 (6)	0.0126 (6)	0.0104 (6)	0.0004 (5)	0.0008 (5)	0.0002 (5)
N4	0.0121 (6)	0.0157 (7)	0.0158 (7)	0.0017 (5)	0.0021 (5)	−0.0027 (5)
C12	0.0169 (7)	0.0143 (8)	0.0124 (7)	0.0000 (6)	0.0009 (6)	0.0024 (6)
C13	0.0151 (7)	0.0182 (8)	0.0123 (7)	−0.0036 (6)	0.0023 (6)	0.0010 (6)
C14	0.0127 (7)	0.0118 (7)	0.0135 (7)	0.0002 (6)	−0.0009 (6)	−0.0001 (6)
N5	0.0121 (6)	0.0115 (6)	0.0124 (6)	−0.0016 (5)	0.0011 (5)	−0.0002 (5)
N6	0.0172 (7)	0.0139 (7)	0.0161 (7)	−0.0062 (6)	−0.0014 (5)	0.0019 (5)
C15	0.0156 (7)	0.0131 (7)	0.0135 (7)	−0.0001 (6)	0.0019 (6)	−0.0009 (6)
C16	0.0200 (8)	0.0130 (8)	0.0147 (7)	−0.0010 (6)	−0.0015 (6)	−0.0014 (6)
C17	0.0131 (7)	0.0158 (8)	0.0151 (7)	−0.0023 (6)	0.0008 (6)	−0.0004 (6)

Co—O2W	2.1064 (11)	N1—C9	1.3204 (19)
Co—N3	2.1076 (13)	N1—C11	1.3825 (19)
Co—N5	2.1124 (13)	N2—C9	1.345 (2)
Co—N1	2.1347 (13)	N2—C10	1.376 (2)
Co—O1	2.1442 (10)	N2—H2N	0.86 (2)
Co—O1W	2.1680 (11)	C9—H9	0.9500
O1W—H1W	0.85 (3)	C10—C11	1.362 (2)
O1W—H2W	0.85 (3)	C10—H10	0.9500
O2W—H3W	0.82 (3)	C11—H11	0.9500
O2W—H4W	0.82 (2)	N3—C14	1.322 (2)
O3W—H5W	0.81 (2)	N3—C12	1.383 (2)
O3W—H6W	0.82 (3)	N4—C14	1.342 (2)
O1—C1	1.2765 (19)	N4—C13	1.369 (2)
O2—C1	1.2471 (19)	N4—H4N	0.85 (2)
O3—C8	1.2738 (18)	C12—C13	1.356 (2)
O4—C8	1.2450 (19)	C12—H12	0.9500
C1—C2	1.511 (2)	C13—H13	0.9500
C2—C3	1.390 (2)	C14—H14	0.9500
C2—C7	1.393 (2)	N5—C17	1.327 (2)
C3—C4	1.387 (2)	N5—C15	1.380 (2)
C3—H3	0.9500	N6—C17	1.337 (2)
C4—C5	1.395 (2)	N6—C16	1.366 (2)
C4—H4	0.9500	N6—H6N	0.84 (2)
C5—C6	1.391 (2)	C15—C16	1.358 (2)
C5—C8	1.509 (2)	C15—H15	0.9500
C6—C7	1.391 (2)	C16—H16	0.9500
C6—H6	0.9500	C17—H17	0.9500
C7—H7	0.9500
O2W—Co—N3	90.33 (5)	O3—C8—C5	117.34 (13)
O2W—Co—N5	92.80 (5)	C9—N1—C11	105.60 (13)
N3—Co—N5	93.56 (5)	C9—N1—Co	126.08 (10)
O2W—Co—N1	87.96 (5)	C11—N1—Co	128.17 (10)
N3—Co—N1	175.12 (5)	C9—N2—C10	107.31 (13)
N5—Co—N1	91.09 (5)	C9—N2—H2N	124.9 (15)
O2W—Co—O1	175.14 (5)	C10—N2—H2N	127.3 (15)
N3—Co—O1	91.44 (4)	N1—C9—N2	111.54 (14)
N5—Co—O1	91.60 (5)	N1—C9—H9	124.2
N1—Co—O1	89.91 (5)	N2—C9—H9	124.2
O2W—Co—O1W	87.05 (5)	C11—C10—N2	106.07 (14)
N3—Co—O1W	85.59 (5)	C11—C10—H10	127.0
N5—Co—O1W	179.13 (5)	N2—C10—H10	127.0
N1—Co—O1W	89.76 (5)	C10—C11—N1	109.48 (14)
O1—Co—O1W	88.57 (4)	C10—C11—H11	125.3
Co—O1W—H1W	101.0 (18)	N1—C11—H11	125.3
Co—O1W—H2W	117.2 (16)	C14—N3—C12	105.64 (13)
H1W—O1W—H2W	104 (2)	C14—N3—Co	123.89 (11)
Co—O2W—H3W	120.8 (17)	C12—N3—Co	130.35 (11)
Co—O2W—H4W	124.3 (16)	C14—N4—C13	107.78 (14)
H3W—O2W—H4W	110 (2)	C14—N4—H4N	126.4 (14)
H5W—O3W—H6W	106 (2)	C13—N4—H4N	125.7 (14)
C1—O1—Co	127.94 (10)	C13—C12—N3	109.42 (14)
O2—C1—O1	125.22 (14)	C13—C12—H12	125.3
O2—C1—C2	118.35 (14)	N3—C12—H12	125.3
O1—C1—C2	116.43 (13)	C12—C13—N4	106.11 (14)
C3—C2—C7	119.42 (14)	C12—C13—H13	126.9
C3—C2—C1	120.70 (14)	N4—C13—H13	126.9
C7—C2—C1	119.87 (14)	N3—C14—N4	111.05 (14)
C4—C3—C2	120.44 (14)	N3—C14—H14	124.5
C4—C3—H3	119.8	N4—C14—H14	124.5
C2—C3—H3	119.8	C17—N5—C15	104.94 (13)
C3—C4—C5	120.18 (14)	C17—N5—Co	127.98 (11)
C3—C4—H4	119.9	C15—N5—Co	125.69 (10)
C5—C4—H4	119.9	C17—N6—C16	108.07 (14)
C6—C5—C4	119.39 (14)	C17—N6—H6N	123.5 (15)
C6—C5—C8	120.01 (14)	C16—N6—H6N	128.1 (15)
C4—C5—C8	120.59 (13)	C16—C15—N5	110.03 (14)
C7—C6—C5	120.30 (15)	C16—C15—H15	125.0
C7—C6—H6	119.9	N5—C15—H15	125.0
C5—C6—H6	119.9	C15—C16—N6	105.63 (14)
C6—C7—C2	120.18 (15)	C15—C16—H16	127.2
C6—C7—H7	119.9	N6—C16—H16	127.2
C2—C7—H7	119.9	N5—C17—N6	111.33 (14)
O4—C8—O3	123.78 (14)	N5—C17—H17	124.3
O4—C8—C5	118.87 (13)	N6—C17—H17	124.3

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1i	0.86 (2)	2.09 (2)	2.9204 (17)	162 (2)
N4—H4N···O3Wii	0.85 (2)	2.18 (2)	2.9842 (18)	157.0 (19)
N4—H4N···O4iii	0.85 (2)	2.50 (2)	2.9521 (18)	114.5 (17)
N6—H6N···O3iv	0.84 (2)	2.02 (2)	2.8249 (18)	162 (2)
O1W—H1W···O2	0.85 (3)	1.79 (3)	2.6160 (16)	163 (3)
O1W—H2W···O4v	0.85 (3)	1.85 (3)	2.6606 (16)	161 (2)
O2W—H3W···O3vi	0.82 (3)	1.95 (3)	2.7516 (16)	168 (2)
O2W—H4W···O3Wvii	0.82 (2)	2.00 (2)	2.8118 (17)	172 (2)
O3W—H5W···O1W	0.81 (2)	2.08 (2)	2.8632 (16)	164 (2)
O3W—H6W···O3vi	0.82 (3)	1.95 (3)	2.7528 (17)	167 (2)

Table 1

Selected geometric parameters (Å, °)

Co—O2W	2.1064 (11)
Co—N3	2.1076 (13)
Co—N5	2.1124 (13)
Co—N1	2.1347 (13)
Co—O1	2.1442 (10)
Co—O1W	2.1680 (11)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1i	0.86 (2)	2.09 (2)	2.9204 (17)	162 (2)
N4—H4N⋯O3Wii	0.85 (2)	2.18 (2)	2.9842 (18)	157.0 (19)
N4—H4N⋯O4iii	0.85 (2)	2.50 (2)	2.9521 (18)	114.5 (17)
N6—H6N⋯O3iv	0.84 (2)	2.02 (2)	2.8249 (18)	162 (2)
O1W—H1W⋯O2	0.85 (3)	1.79 (3)	2.6160 (16)	163 (3)
O1W—H2W⋯O4v	0.85 (3)	1.85 (3)	2.6606 (16)	161 (2)
O2W—H3W⋯O3vi	0.82 (3)	1.95 (3)	2.7516 (16)	168 (2)
O2W—H4W⋯O3Wvii	0.82 (2)	2.00 (2)	2.8118 (17)	172 (2)
O3W—H5W⋯O1W	0.81 (2)	2.08 (2)	2.8632 (16)	164 (2)
O3W—H6W⋯O3vi	0.82 (3)	1.95 (3)	2.7528 (17)	167 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .