catena-Poly[[diaqua­bis(methanol)cobalt(II)]-μ-phthalato]

In the crystal structure of the polymeric title compound, [Co(μ-C₈H₄O₄)(CH₃OH)₂(H₂O)₂]_n, two independent Co^II atoms both occupy special positions with site symmetry. Each Co^II atom assumes a distorted octa­hedral coordination geometry. The phthalate anion acts as a bridging ligand and leads to the formation of a zigzag chain running along the c axis. O—H...O and C—H...O hydrogen bonds connect the chains and result in the formation of a three-dimensional structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.076
• wR factor = 0.133
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.19 Ratio

Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.06 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         O7
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (9)       1.53
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co2         (9)       1.45
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          8

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

   2 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
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Phthalate anion is a versatile ligand and a large number of multi-nuclear complexes with it as a bridging ligand have been reported (Baca et al., 2003, 2006). Here we report the crystal structure of a novel coordination polymer dealing with phthalate anion, (I).

Fig. 1 shows the asymmetric unit and the symmetry-related fragment of (I). Atoms Co1 and Co2 lie in an inversion centre and are in a distorted octahedral CoO₆ coordination geometry (Table 1). Each phthalate anion as a µ₂-bridging ligand joins two adjacent Co^II atoms with separation of 6.6367 (6) Å and it results in the formation of a zigzag one-dimensional chain along the c axis. The overall crystal structure of (I) is a super-molecular three-dimensional network, which attributes to the connection between chains by the O—H···O and C—H···O hydrogen bonds (Table 2 and Fig. 2).

Related literature

For related crystal structures, see: Baca et al. (2003, 2006).

S2. Experimental

A methanol solution (50 ml) containing phthalic acid (3.32 g, 0.02 mol) and cobalt acetate (1.77 g, 0.01 mol) was refluxed for 50 min and the reaction solid was separated and dried. The dried solid (0.2 g) was dissolved in H₂O (20 ml) and pink single crystals were obtained after the solution had been allowed to stand at room temperature for about a month.

S3. Refinement

H atoms of water molecules and hydroxyl groups were located in a difference Fourier map and were refined with distance restraints of O—H = 0.85 (2) Å for water molecules and 0.82 (2) Å for hydroxyl groups, and with U_iso(H) = 1.5U_eq(O). Other H atoms were placed in calculated positions (C—H = 0.93 or 0.96 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The coordination structure of (I), with the atom numbering scheme and thermal ellipsoids drawn at the 30% probability level [symmetry codes: (i) -x + 1, -y, -z + 2; (ii) -x + 1, -y, -z + 1].
	Fig. 2. A packing diagram of (I), showing hydrogen bonds (dashed lines).

catena-Poly[[diaquabis(methanol)cobalt(II)]-µ-phthalato]

Crystal data

[Co(C8H4O4)(CH4O)2(H2O)2]	F(000) = 668
Mr = 323.16	Dx = 1.613 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2648 reflections
a = 10.0810 (9) Å	θ = 2.6–27.6°
b = 9.9429 (9) Å	µ = 1.32 mm^−1
c = 13.2735 (12) Å	T = 293 K
β = 90.300 (2)°	Prism, pink
V = 1330.4 (2) Å^3	0.20 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	2351 independent reflections
Radiation source: fine-focus sealed tube	2172 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 25.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→12
Tmin = 0.778, Tmax = 0.826	k = −11→11
5378 measured reflections	l = −15→15

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	w = 1/[σ^2(Fo^2) + (0.0199P)^2 + 5.7387P] where P = (Fo^2 + 2Fc^2)/3
2351 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.49 e Å^−3
8 restraints	Δρmin = −0.30 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
Co1	0.5000	0.0000	1.0000	0.0270 (3)
Co2	0.5000	0.0000	0.5000	0.0291 (3)
O1	0.3636 (3)	0.1108 (3)	0.9162 (3)	0.0247 (8)
O2	0.1792 (4)	−0.0057 (4)	0.9467 (3)	0.0421 (10)
O3	0.4035 (4)	0.1133 (4)	0.6087 (3)	0.0316 (9)
O4	0.3505 (4)	−0.0417 (3)	0.7224 (3)	0.0304 (9)
O5	0.6557 (4)	0.1154 (4)	0.9317 (3)	0.0352 (9)
H2	0.717 (5)	0.087 (7)	0.966 (4)	0.053*
O6	0.5027 (5)	0.1347 (4)	1.1156 (3)	0.0374 (10)
H6C	0.553 (5)	0.120 (6)	1.166 (3)	0.056*
H6D	0.471 (6)	0.214 (3)	1.117 (4)	0.056*
O7	0.6667 (4)	0.1246 (4)	0.5157 (4)	0.0459 (11)
H1	0.661 (8)	0.198 (4)	0.488 (5)	0.069*
O8	0.4320 (4)	0.1280 (4)	0.3867 (3)	0.0343 (10)
H8A	0.412 (6)	0.210 (3)	0.388 (5)	0.051*
H8B	0.499 (4)	0.115 (5)	0.349 (4)	0.051*
C1	0.2433 (5)	0.0782 (5)	0.8981 (4)	0.0250 (12)
C2	0.1755 (5)	0.1554 (5)	0.8149 (4)	0.0273 (12)
C3	0.0660 (6)	0.2309 (6)	0.8391 (5)	0.0417 (15)
H3A	0.0314	0.2250	0.9037	0.050*
C4	0.0059 (6)	0.3155 (7)	0.7695 (5)	0.0482 (18)
H4A	−0.0682	0.3658	0.7871	0.058*
C5	0.0578 (6)	0.3241 (6)	0.6739 (5)	0.0460 (17)
H5A	0.0200	0.3822	0.6270	0.055*
C6	0.1661 (6)	0.2462 (6)	0.6475 (5)	0.0400 (14)
H6B	0.1996	0.2512	0.5825	0.048*
C7	0.2251 (5)	0.1606 (5)	0.7175 (4)	0.0267 (12)
C8	0.3358 (5)	0.0702 (5)	0.6825 (4)	0.0236 (12)
C9	0.6831 (7)	0.1107 (7)	0.8252 (5)	0.0537 (18)
H9A	0.7566	0.1687	0.8104	0.080*
H9B	0.6064	0.1400	0.7882	0.080*
H9C	0.7047	0.0202	0.8062	0.080*
C10	0.7954 (9)	0.0949 (10)	0.5518 (8)	0.098 (4)
H10A	0.8493	0.1743	0.5489	0.147*
H10B	0.8341	0.0259	0.5108	0.147*
H10C	0.7902	0.0642	0.6202	0.147*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0288 (6)	0.0185 (5)	0.0336 (6)	−0.0006 (5)	−0.0035 (4)	0.0013 (5)
Co2	0.0353 (6)	0.0198 (5)	0.0321 (6)	0.0021 (5)	0.0001 (5)	−0.0005 (5)
O1	0.0189 (19)	0.0197 (18)	0.035 (2)	−0.0017 (15)	−0.0050 (15)	0.0037 (16)
O2	0.037 (2)	0.043 (2)	0.045 (2)	−0.012 (2)	−0.0051 (19)	0.015 (2)
O3	0.044 (2)	0.0190 (19)	0.032 (2)	0.0042 (18)	0.0052 (18)	−0.0024 (16)
O4	0.051 (3)	0.0164 (19)	0.0236 (19)	0.0067 (17)	0.0021 (18)	0.0000 (15)
O5	0.032 (2)	0.034 (2)	0.040 (2)	−0.0033 (19)	−0.0020 (18)	0.0073 (19)
O6	0.055 (3)	0.022 (2)	0.035 (2)	0.011 (2)	−0.011 (2)	−0.0040 (18)
O7	0.039 (3)	0.022 (2)	0.076 (3)	−0.002 (2)	−0.011 (2)	0.005 (2)
O8	0.041 (3)	0.023 (2)	0.038 (2)	0.0115 (19)	0.0017 (19)	0.0029 (18)
C1	0.029 (3)	0.021 (3)	0.025 (3)	0.002 (2)	−0.002 (2)	−0.004 (2)
C2	0.023 (3)	0.024 (3)	0.035 (3)	0.000 (2)	−0.003 (2)	−0.003 (2)
C3	0.032 (3)	0.046 (4)	0.046 (4)	0.013 (3)	0.003 (3)	−0.002 (3)
C4	0.032 (3)	0.050 (4)	0.063 (5)	0.021 (3)	−0.002 (3)	−0.005 (3)
C5	0.043 (4)	0.038 (4)	0.057 (4)	0.011 (3)	−0.012 (3)	0.010 (3)
C6	0.042 (4)	0.034 (3)	0.043 (3)	0.002 (3)	−0.005 (3)	0.009 (3)
C7	0.026 (3)	0.017 (3)	0.037 (3)	−0.001 (2)	−0.002 (2)	−0.002 (2)
C8	0.037 (3)	0.019 (3)	0.014 (2)	−0.001 (2)	−0.007 (2)	0.004 (2)
C9	0.057 (5)	0.037 (4)	0.067 (5)	−0.002 (3)	0.008 (4)	0.009 (4)
C10	0.074 (6)	0.102 (8)	0.118 (8)	−0.039 (6)	−0.034 (6)	0.048 (7)

Geometric parameters (Å, º)

Co1—O1^i	2.080 (3)	O7—H1	0.82 (5)
Co1—O1	2.080 (3)	O8—H8A	0.84 (3)
Co1—O5^i	2.148 (4)	O8—H8B	0.85 (4)
Co1—O5	2.148 (4)	C1—C2	1.506 (7)
Co1—O6	2.037 (4)	C2—C3	1.374 (8)
Co1—O6^i	2.037 (4)	C2—C7	1.389 (8)
Co2—O3	2.077 (4)	C3—C4	1.386 (9)
Co2—O3^ii	2.077 (4)	C3—H3A	0.9300
Co2—O7	2.098 (4)	C4—C5	1.377 (9)
Co2—O7^ii	2.098 (4)	C4—H4A	0.9300
Co2—O8^ii	2.083 (4)	C5—C6	1.385 (9)
Co2—O8	2.083 (4)	C5—H5A	0.9300
O1—C1	1.277 (6)	C6—C7	1.392 (8)
O2—C1	1.239 (6)	C6—H6B	0.9300
O3—C8	1.271 (6)	C7—C8	1.508 (7)
O4—C8	1.240 (6)	C9—H9A	0.9600
O5—C9	1.443 (8)	C9—H9B	0.9600
O5—H2	0.82 (5)	C9—H9C	0.9600
O6—H6C	0.85 (4)	C10—H10A	0.9600
O6—H6D	0.85 (5)	C10—H10B	0.9600
O7—C10	1.411 (9)	C10—H10C	0.9600
O6—Co1—O6^i	180.000 (1)	Co2—O7—H1	115 (5)
O6—Co1—O1^i	86.52 (15)	Co2—O8—H8A	131 (4)
O6^i—Co1—O1^i	93.48 (15)	Co2—O8—H8B	94 (4)
O6—Co1—O1	93.48 (15)	H8A—O8—H8B	110 (3)
O6^i—Co1—O1	86.52 (15)	O2—C1—O1	124.8 (5)
O1^i—Co1—O1	180.000 (1)	O2—C1—C2	119.3 (5)
O6—Co1—O5^i	92.29 (17)	O1—C1—C2	115.8 (5)
O6^i—Co1—O5^i	87.71 (17)	C3—C2—C7	119.4 (5)
O1^i—Co1—O5^i	88.50 (14)	C3—C2—C1	118.0 (5)
O1—Co1—O5^i	91.50 (14)	C7—C2—C1	122.4 (5)
O6—Co1—O5	87.71 (17)	C2—C3—C4	121.6 (6)
O6^i—Co1—O5	92.29 (17)	C2—C3—H3A	119.2
O1^i—Co1—O5	91.50 (14)	C4—C3—H3A	119.2
O1—Co1—O5	88.50 (14)	C5—C4—C3	119.0 (6)
O5^i—Co1—O5	180.0	C5—C4—H4A	120.5
O3—Co2—O3^ii	180.00 (14)	C3—C4—H4A	120.5
O3—Co2—O8^ii	89.05 (15)	C4—C5—C6	120.2 (6)
O3^ii—Co2—O8^ii	90.95 (15)	C4—C5—H5A	119.9
O3—Co2—O8	90.95 (15)	C6—C5—H5A	119.9
O3^ii—Co2—O8	89.05 (15)	C5—C6—C7	120.5 (6)
O8^ii—Co2—O8	180.00 (15)	C5—C6—H6B	119.8
O3—Co2—O7	89.33 (17)	C7—C6—H6B	119.8
O3^ii—Co2—O7	90.67 (17)	C2—C7—C6	119.3 (5)
O8^ii—Co2—O7	91.63 (17)	C2—C7—C8	122.4 (5)
O8—Co2—O7	88.37 (17)	C6—C7—C8	118.2 (5)
O3—Co2—O7^ii	90.67 (17)	O4—C8—O3	124.6 (5)
O3^ii—Co2—O7^ii	89.33 (17)	O4—C8—C7	119.3 (5)
O8^ii—Co2—O7^ii	88.37 (17)	O3—C8—C7	115.9 (4)
O8—Co2—O7^ii	91.63 (17)	O5—C9—H9A	109.5
O7—Co2—O7^ii	180.00 (18)	O5—C9—H9B	109.5
C1—O1—Co1	126.2 (3)	H9A—C9—H9B	109.5
C8—O3—Co2	127.4 (3)	O5—C9—H9C	109.5
C9—O5—Co1	122.7 (4)	H9A—C9—H9C	109.5
C9—O5—H2	113 (5)	H9B—C9—H9C	109.5
Co1—O5—H2	98 (5)	O7—C10—H10A	109.5
Co1—O6—H6C	119 (4)	O7—C10—H10B	109.5
Co1—O6—H6D	128 (4)	H10A—C10—H10B	109.5
H6C—O6—H6D	112 (3)	O7—C10—H10C	109.5
C10—O7—Co2	130.1 (5)	H10A—C10—H10C	109.5
C10—O7—H1	114 (6)	H10B—C10—H10C	109.5
O6—Co1—O1—C1	−110.5 (4)	O2—C1—C2—C7	−126.5 (6)
O6^i—Co1—O1—C1	69.5 (4)	O1—C1—C2—C7	56.9 (7)
O5^i—Co1—O1—C1	−18.1 (4)	C7—C2—C3—C4	−2.0 (9)
O5—Co1—O1—C1	161.9 (4)	C1—C2—C3—C4	173.3 (6)
O8^ii—Co2—O3—C8	−43.5 (4)	C2—C3—C4—C5	−0.1 (10)
O8—Co2—O3—C8	136.5 (4)	C3—C4—C5—C6	1.7 (10)
O7—Co2—O3—C8	−135.1 (4)	C4—C5—C6—C7	−1.2 (10)
O7^ii—Co2—O3—C8	44.9 (4)	C3—C2—C7—C6	2.6 (8)
O6—Co1—O5—C9	−158.0 (4)	C1—C2—C7—C6	−172.6 (5)
O6^i—Co1—O5—C9	22.0 (4)	C3—C2—C7—C8	−173.6 (5)
O1^i—Co1—O5—C9	115.6 (4)	C1—C2—C7—C8	11.3 (8)
O1—Co1—O5—C9	−64.4 (4)	C5—C6—C7—C2	−1.0 (9)
O3—Co2—O7—C10	114.6 (7)	C5—C6—C7—C8	175.3 (5)
O3^ii—Co2—O7—C10	−65.4 (7)	Co2—O3—C8—O4	25.4 (7)
O8^ii—Co2—O7—C10	25.6 (7)	Co2—O3—C8—C7	−150.5 (4)
O8—Co2—O7—C10	−154.4 (7)	C2—C7—C8—O4	28.2 (8)
Co1—O1—C1—O2	18.8 (8)	C6—C7—C8—O4	−148.0 (5)
Co1—O1—C1—C2	−164.9 (3)	C2—C7—C8—O3	−155.7 (5)
O2—C1—C2—C3	58.3 (7)	C6—C7—C8—O3	28.1 (7)
O1—C1—C2—C3	−118.3 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H2···O2^i	0.82 (5)	1.75 (6)	2.557 (5)	167 (7)
O7—H1···O5^iii	0.82 (5)	2.00 (5)	2.817 (6)	175 (8)
O6—H6C···O4^i	0.85 (5)	1.93 (5)	2.764 (5)	165 (6)
O6—H6D···O3^iv	0.85 (4)	1.85 (4)	2.699 (5)	176 (6)
O8—H8A···O1^iii	0.84 (3)	1.88 (3)	2.716 (5)	170 (6)
O8—H8B···O4^ii	0.85 (4)	1.94 (5)	2.770 (5)	166 (5)
C5—H5A···O2^v	0.93	2.49	3.331 (7)	150

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