catena-poly­[[[tetra­aqua­cobalt(II)]-μ-4,4′-bi­pyridine-κ²N:N′] phthalate dihydrate]

A polymeric cobalt complex, {[Co(C₁₀H₈N₂)(H₂O)₄](C₈H₄O₄)·2H₂O}_n, was synthesized and its crystal structure has been determined by X-ray diffraction. The complex exhibits a polymeric structure consisting of six-coordinated Co^II units linked via 4,4′-bi­pyridine (4,4′-bpy) to form a linear chain. The asymmetric unit contains only one half-mol­ecule of the bridging ligand and two coordinated water molecules, the Co^II ion and the bridging ligand lying on a twofold rotation axis. Each cobalt(II) ion is in a distorted octahedral environment with a CoN₂O₄ core; 4,4′-bpy acts as a bridging ligand and four O atoms from coordinated water mol­ecules act as terminal ligands. The chains are linked to (which also lie on twofold axes) uncoordinated phthalate anions and water mol­ecules by extensive hydrogen bonds to form a three-dimensional supramolecular structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.084
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.04
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            N2  -CO1 -N1  -C1     37.00  0.80   1.545   1.555   1.555   1.555

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C18 H24 Co1 N2 O10
            Atom count from the _atom_site data:  C18 H24.04 Co1 N2 O10
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: check formula stoichiometry or atom site occupancies.
           From the CIF: _cell_formula_units_Z    2
           From the CIF: _chemical_formula_sum  C18 H24 Co N2 O10
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         36.00     36.00    0.00
           H         48.00     48.08   -0.08
           Co         2.00      2.00    0.00
           N          4.00      4.00    0.00
           O         20.00     20.00    0.00

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

catena-poly[[[tetraaquacobalt(II)]-µ-4,4-bipyridine-κ²N:N'] phthalate dihydrate]

Crystal data

[Co(C10H8N2)(H2O)4](C8H4O4)·2H2O	F(000) = 506
Mr = 487.32	Dx = 1.573 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.511 (3) Å	Cell parameters from 925 reflections
b = 11.496 (3) Å	θ = 2.8–26.1°
c = 11.528 (4) Å	µ = 0.89 mm^−1
β = 125.287 (5)°	T = 293 K
V = 1028.9 (5) Å^3	Block, red
Z = 2	0.18 × 0.16 × 0.12 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2111 independent reflections
Radiation source: fine-focus sealed tube	1665 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→11
Tmin = 0.794, Tmax = 0.898	k = −13→14
5821 measured reflections	l = −14→9

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0379P)^2 + 0.3271P] where P = (Fo^2 + 2Fc^2)/3
2111 reflections	(Δ/σ)max = 0.001
161 parameters	Δρmax = 0.30 e Å^−3
12 restraints	Δρmin = −0.33 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	Occ. (<1)
Co1	0.5000	0.01953 (4)	0.2500	0.02130 (14)
N1	0.5000	0.2085 (2)	0.2500	0.0250 (6)
N2	0.5000	0.8285 (2)	0.2500	0.0248 (6)
C1	0.5956 (3)	0.2703 (2)	0.2216 (3)	0.0359 (6)
H1	0.6631	0.2300	0.2007	0.043*
C2	0.6003 (3)	0.3895 (2)	0.2214 (3)	0.0357 (6)
H2	0.6709	0.4274	0.2021	0.043*
C3	0.5000	0.4538 (3)	0.2500	0.0239 (7)
C4	0.5000	0.5825 (3)	0.2500	0.0238 (7)
C5	0.5586 (3)	0.6475 (2)	0.1838 (3)	0.0299 (6)
H5	0.5996	0.6097	0.1375	0.036*
C6	0.5564 (3)	0.7664 (2)	0.1864 (3)	0.0306 (6)
H6	0.5967	0.8066	0.1411	0.037*
O1	0.1812 (3)	0.12805 (17)	0.3772 (2)	0.0464 (5)
O2	0.0753 (3)	0.17483 (19)	0.4985 (2)	0.0534 (6)
C7	0.1002 (3)	0.1938 (2)	0.4056 (3)	0.0298 (6)
C8	0.0389 (3)	0.3059 (2)	0.3227 (2)	0.0265 (5)
C9	0.0755 (3)	0.4109 (2)	0.3942 (3)	0.0410 (7)
H9	0.1260	0.4113	0.4914	0.049*
C10	0.0374 (4)	0.5152 (2)	0.3215 (4)	0.0544 (8)
H10	0.0627	0.5853	0.3701	0.065*
O3	0.6092 (2)	0.02703 (15)	0.46407 (17)	0.0325 (4)
H3A	0.524 (3)	0.021 (3)	0.469 (4)	0.049*	0.67
H3B	0.657 (3)	0.0934 (12)	0.493 (3)	0.049*	0.67
H3C	0.683 (3)	−0.0262 (18)	0.512 (3)	0.049*	0.67
O4	0.2463 (2)	0.00320 (15)	0.19401 (19)	0.0377 (4)
H4A	0.1831	0.0464	0.2059	0.057*
H4B	0.1875	−0.0500	0.1335	0.057*
O5	0.8740 (3)	0.19927 (18)	0.6005 (2)	0.0602 (6)
H5A	0.917 (5)	0.209 (4)	0.554 (3)	0.090*	0.67
H5B	0.954 (4)	0.189 (4)	0.6880 (11)	0.090*	0.67
H5C	0.807 (5)	0.141 (2)	0.568 (4)	0.090*	0.67

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0291 (3)	0.0144 (2)	0.0255 (2)	0.000	0.0188 (2)	0.000
N1	0.0327 (15)	0.0170 (14)	0.0297 (15)	0.000	0.0205 (13)	0.000
N2	0.0293 (15)	0.0195 (15)	0.0293 (15)	0.000	0.0190 (13)	0.000
C1	0.0491 (16)	0.0203 (13)	0.0623 (18)	0.0051 (11)	0.0461 (15)	0.0026 (12)
C2	0.0455 (16)	0.0226 (13)	0.0619 (18)	0.0004 (11)	0.0442 (15)	0.0036 (12)
C3	0.0278 (17)	0.0141 (17)	0.0294 (17)	0.000	0.0164 (15)	0.000
C4	0.0267 (18)	0.0162 (17)	0.0291 (18)	0.000	0.0165 (15)	0.000
C5	0.0444 (15)	0.0200 (12)	0.0408 (14)	0.0012 (10)	0.0336 (13)	−0.0017 (10)
C6	0.0449 (15)	0.0208 (13)	0.0416 (14)	−0.0005 (10)	0.0340 (13)	0.0022 (10)
O1	0.0621 (13)	0.0441 (12)	0.0460 (12)	0.0268 (10)	0.0388 (11)	0.0178 (9)
O2	0.0669 (14)	0.0611 (14)	0.0591 (14)	0.0206 (11)	0.0520 (13)	0.0241 (11)
C7	0.0274 (13)	0.0299 (14)	0.0311 (13)	−0.0005 (10)	0.0162 (12)	0.0027 (10)
C8	0.0229 (12)	0.0254 (12)	0.0327 (13)	−0.0008 (9)	0.0170 (11)	−0.0001 (10)
C9	0.0378 (16)	0.0392 (17)	0.0445 (16)	−0.0049 (12)	0.0229 (14)	−0.0132 (12)
C10	0.062 (2)	0.0250 (14)	0.079 (2)	−0.0082 (14)	0.043 (2)	−0.0149 (14)
O3	0.0447 (10)	0.0280 (9)	0.0294 (9)	0.0057 (8)	0.0241 (9)	0.0021 (8)
O4	0.0339 (9)	0.0352 (11)	0.0516 (11)	−0.0002 (7)	0.0291 (9)	−0.0095 (8)
O5	0.0766 (16)	0.0515 (14)	0.0757 (16)	−0.0205 (12)	0.0574 (14)	−0.0207 (12)

Geometric parameters (Å, º)

Co1—O3^i	2.0529 (17)	C5—H5	0.9300
Co1—O3	2.0529 (17)	C6—H6	0.9300
Co1—O4	2.1158 (17)	O1—C7	1.250 (3)
Co1—O4^i	2.1158 (17)	O2—C7	1.242 (3)
Co1—N1	2.173 (3)	C7—C8	1.507 (3)
Co1—N2^ii	2.197 (3)	C8—C8^iv	1.387 (5)
N1—C1^i	1.334 (3)	C8—C9	1.388 (3)
N1—C1	1.334 (3)	C9—C10	1.386 (4)
N2—C6	1.337 (3)	C9—H9	0.9300
N2—C6^i	1.337 (3)	C10—C10^iv	1.368 (7)
N2—Co1^iii	2.197 (3)	C10—H10	0.9300
C1—C2	1.371 (3)	O3—H3A	0.8499 (11)
C1—H1	0.9300	O3—H3B	0.8499 (11)
C2—C3	1.388 (3)	O3—H3C	0.8502 (11)
C2—H2	0.9300	O4—H4A	0.8499
C3—C2^i	1.388 (3)	O4—H4B	0.8499
C3—C4	1.480 (4)	O5—H5A	0.8501 (11)
C4—C5^i	1.394 (3)	O5—H5B	0.8501 (11)
C4—C5	1.394 (3)	O5—H5C	0.8501 (11)
C5—C6	1.368 (3)
O3^i—Co1—O3	175.18 (10)	C5—C4—C3	122.38 (15)
O3^i—Co1—O4	86.62 (7)	C6—C5—C4	120.4 (2)
O3—Co1—O4	93.81 (7)	C6—C5—H5	119.8
O3^i—Co1—O4^i	93.81 (7)	C4—C5—H5	119.8
O3—Co1—O4^i	86.62 (7)	N2—C6—C5	124.2 (2)
O4—Co1—O4^i	169.82 (9)	N2—C6—H6	117.9
O3^i—Co1—N1	87.59 (5)	C5—C6—H6	117.9
O3—Co1—N1	87.59 (5)	O2—C7—O1	125.0 (2)
O4—Co1—N1	95.09 (5)	O2—C7—C8	120.0 (2)
O4^i—Co1—N1	95.09 (5)	O1—C7—C8	115.0 (2)
O3^i—Co1—N2^ii	92.41 (5)	C8^iv—C8—C9	119.56 (16)
O3—Co1—N2^ii	92.41 (5)	C8^iv—C8—C7	120.48 (14)
O4—Co1—N2^ii	84.91 (5)	C9—C8—C7	119.7 (2)
O4^i—Co1—N2^ii	84.91 (5)	C10—C9—C8	120.3 (3)
N1—Co1—N2^ii	180.0	C10—C9—H9	119.8
C1^i—N1—C1	115.7 (3)	C8—C9—H9	119.8
C1^i—N1—Co1	122.14 (14)	C10^iv—C10—C9	120.09 (17)
C1—N1—Co1	122.14 (14)	C10^iv—C10—H10	120.0
C6—N2—C6^i	115.5 (3)	C9—C10—H10	120.0
C6—N2—Co1^iii	122.27 (14)	Co1—O3—H3A	104 (2)
C6^i—N2—Co1^iii	122.27 (14)	Co1—O3—H3B	107 (2)
N1—C1—C2	124.0 (2)	H3A—O3—H3B	111.3 (12)
N1—C1—H1	118.0	Co1—O3—H3C	114 (2)
C2—C1—H1	118.0	H3A—O3—H3C	110.4 (12)
C1—C2—C3	120.3 (2)	H3B—O3—H3C	110.0 (12)
C1—C2—H2	119.9	Co1—O4—H4A	133.4
C3—C2—H2	119.9	Co1—O4—H4B	114.1
C2^i—C3—C2	115.7 (3)	H4A—O4—H4B	111.2
C2^i—C3—C4	122.17 (15)	H5A—O5—H5B	110.0 (12)
C2—C3—C4	122.17 (15)	H5A—O5—H5C	110.0 (12)
C5^i—C4—C5	115.2 (3)	H5B—O5—H5C	109.9 (12)
C5^i—C4—C3	122.38 (15)
O3^i—Co1—N1—C1^i	114.54 (15)	C2—C3—C4—C5^i	−161.26 (18)
O3—Co1—N1—C1^i	−65.46 (15)	C2^i—C3—C4—C5	−161.27 (18)
O4—Co1—N1—C1^i	28.15 (15)	C2—C3—C4—C5	18.73 (18)
O4^i—Co1—N1—C1^i	−151.85 (15)	C5^i—C4—C5—C6	0.03 (17)
O3^i—Co1—N1—C1	−65.46 (15)	C3—C4—C5—C6	−179.97 (17)
O3—Co1—N1—C1	114.54 (15)	C6^i—N2—C6—C5	0.03 (18)
O4—Co1—N1—C1	−151.85 (15)	Co1^iii—N2—C6—C5	−179.97 (18)
O4^i—Co1—N1—C1	28.15 (15)	C4—C5—C6—N2	−0.1 (4)
N2^ii—Co1—N1—C1	37.0 (8)	O2—C7—C8—C8^iv	−137.9 (3)
C1^i—N1—C1—C2	0.5 (2)	O1—C7—C8—C8^iv	45.1 (4)
Co1—N1—C1—C2	−179.5 (2)	O2—C7—C8—C9	48.5 (3)
N1—C1—C2—C3	−0.9 (4)	O1—C7—C8—C9	−128.6 (3)
C1—C2—C3—C2^i	0.43 (19)	C8^iv—C8—C9—C10	−1.0 (4)
C1—C2—C3—C4	−179.57 (19)	C7—C8—C9—C10	172.7 (2)
C2^i—C3—C4—C5^i	18.73 (18)	C8—C9—C10—C10^iv	0.2 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5C···O3	0.85 (1)	2.02 (1)	2.856 (3)	168 (4)
O5—H5B···O5^v	0.85 (1)	2.01 (1)	2.843 (5)	167 (4)
O5—H5A···O2^vi	0.85 (1)	1.98 (2)	2.780 (3)	156 (4)
O4—H4B···O2^vii	0.85	1.92	2.771 (3)	174
O3—H3C···O1^viii	0.85 (1)	1.66 (1)	2.507 (2)	172 (3)
O3—H3B···O5	0.85 (1)	2.08 (2)	2.856 (3)	151 (3)
O3—H3A···O3^viii	0.85 (1)	1.90 (1)	2.716 (3)	159 (3)

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