Poly[[[diaqua­bis(pyridine-4-carboxamide-κN¹)cobalt(II)]-μ₂-squarato-κO:O′] dihydrate]

The title polymeric compound, {[Co(C₄O₄)(C₆H₆N₂O)₂(H₂O)₂]·2H₂O}_n, has two crystallographically independent half-mol­ecules in the asymmetric unit, each Co atom residing on a center of symmetry. The two polymeric chains exhibit similar coordination geometry but display differences with regard to other structural features. Each Co^II center is octa­hedrally coordinated by two mutually trans pyridine-4-carboxamide (or isonicotinamide) ligands, two mutually trans squarate ligands and two trans aqua ligands. The crystal structure contains chains of squarate-1,3-bridged Co^II ions. These chains are held together by N—H...O and O—H...O inter­molecular hydrogen-bond inter­actions, forming an extensive three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.056
• wR factor = 0.164
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Poly[[[diaquabis(pyridine-4-carboxamide-κN¹)cobalt(II)]-µ₂– squarato-κO:O'] dihydrate]

Crystal data

[Co(C4O4)(C6H6N2O)2(H2O)2]·2H2O	Z = 2
Mr = 487.29	F(000) = 502
Triclinic, P1	Dx = 1.622 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1578 (8) Å	Cell parameters from 5876 reflections
b = 10.8246 (12) Å	θ = 2.3–27.3°
c = 12.1665 (11) Å	µ = 0.92 mm^−1
α = 75.445 (8)°	T = 297 K
β = 89.690 (8)°	Prism, pink
γ = 74.082 (8)°	0.3 × 0.2 × 0.1 mm
V = 997.68 (17) Å^3

Data collection

Stoe IPDS-II diffractometer	4333 independent reflections
Radiation source: fine-focus sealed tube	3003 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 6.67 pixels mm^-1	θmax = 27.0°, θmin = 2.3°
ω scans	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.710, Tmax = 0.899	l = −15→15
20174 measured reflections

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1027P)^2] where P = (Fo^2 + 2Fc^2)/3
4333 reflections	(Δ/σ)max = 0.017
319 parameters	Δρmax = 1.12 e Å^−3
17 restraints	Δρmin = −0.81 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	0.5000	0.5000	0.02440 (19)
Co2	0.0000	0.5000	0.0000	0.02526 (19)
C1	0.7041 (5)	0.2259 (4)	0.4716 (4)	0.0459 (10)
H1	0.7484	0.2781	0.4131	0.055*
C2	0.7604 (6)	0.0896 (4)	0.4909 (4)	0.0504 (11)
H2	0.8409	0.0517	0.4456	0.060*
C3	0.6978 (5)	0.0093 (4)	0.5771 (3)	0.0396 (9)
C4	0.5784 (6)	0.0713 (4)	0.6417 (4)	0.0485 (10)
H4	0.5325	0.0210	0.7007	0.058*
C5	0.5280 (6)	0.2085 (4)	0.6176 (4)	0.0474 (10)
H5	0.4481	0.2487	0.6620	0.057*
C6	0.7645 (6)	−0.1387 (5)	0.5972 (4)	0.0503 (10)
C7	0.8808 (4)	0.5051 (4)	0.4691 (3)	0.0306 (7)
C8	0.9578 (4)	0.4929 (4)	0.5799 (3)	0.0307 (7)
C9	0.2130 (5)	0.2242 (4)	−0.0206 (4)	0.0481 (10)
H9	0.2678	0.2758	−0.0724	0.058*
C10	0.2665 (6)	0.0875 (5)	−0.0025 (4)	0.0520 (11)
H10	0.3552	0.0487	−0.0422	0.062*
C11	0.1879 (5)	0.0079 (4)	0.0748 (3)	0.0392 (9)
C12	0.0584 (5)	0.0715 (4)	0.1318 (4)	0.0467 (10)
H12	0.0042	0.0223	0.1861	0.056*
C13	0.0100 (5)	0.2074 (4)	0.1077 (4)	0.0459 (10)
H13	−0.0805	0.2482	0.1450	0.055*
C14	0.2468 (6)	−0.1394 (4)	0.0919 (4)	0.0476 (10)
C15	0.3817 (4)	0.4992 (4)	0.0308 (3)	0.0321 (8)
C16	0.4442 (4)	0.5358 (4)	−0.0811 (3)	0.0327 (8)
N1	0.5883 (4)	0.2862 (3)	0.5338 (3)	0.0343 (7)
N2	0.7076 (6)	−0.2149 (4)	0.6823 (4)	0.0619 (11)
H2A	0.627 (6)	−0.191 (6)	0.729 (5)	0.093*
H2B	0.744 (7)	−0.305 (3)	0.696 (5)	0.093*
N3	0.0852 (4)	0.2850 (3)	0.0337 (3)	0.0357 (7)
N4	0.1635 (6)	−0.2128 (4)	0.1617 (4)	0.0591 (10)
H4A	0.100 (7)	−0.188 (5)	0.215 (4)	0.089*
H4B	0.225 (7)	−0.295 (3)	0.189 (5)	0.089*
O1	0.5814 (3)	0.4837 (3)	0.6642 (2)	0.0419 (7)
H1A	0.680 (4)	0.493 (5)	0.677 (4)	0.063*
H1B	0.512 (5)	0.512 (5)	0.713 (4)	0.063*
O2	0.7364 (3)	0.5100 (3)	0.4288 (2)	0.0364 (6)
O3	0.9030 (3)	0.4853 (3)	0.6776 (2)	0.0462 (8)
O4	0.8722 (6)	−0.1858 (4)	0.5367 (4)	0.0806 (12)
O5	0.2410 (3)	0.4965 (3)	0.0716 (2)	0.0408 (7)
O6	0.3778 (3)	0.5832 (3)	−0.1820 (2)	0.0460 (7)
O7	0.0849 (3)	0.5145 (3)	−0.1597 (2)	0.0443 (7)
H7A	0.168 (5)	0.538 (5)	−0.193 (4)	0.066*
H7B	0.014 (5)	0.500 (5)	−0.206 (4)	0.066*
O8	0.3681 (5)	−0.1891 (4)	0.0405 (4)	0.0663 (10)
O9	0.6108 (6)	0.1406 (5)	0.1938 (4)	0.0769 (11)
H9A	0.600 (10)	0.143 (8)	0.125 (4)	0.115*
H9B	0.611 (10)	0.216 (5)	0.200 (7)	0.115*
O10	0.1339 (8)	0.1341 (6)	0.7033 (5)	0.1021 (16)
H10A	0.066 (11)	0.150 (10)	0.643 (6)	0.153*
H10B	0.207 (10)	0.058 (6)	0.722 (8)	0.153*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0170 (3)	0.0354 (4)	0.0235 (3)	−0.0100 (2)	0.0027 (2)	−0.0096 (3)
Co2	0.0179 (3)	0.0386 (4)	0.0235 (3)	−0.0119 (3)	0.0032 (2)	−0.0114 (3)
C1	0.049 (2)	0.042 (2)	0.048 (2)	−0.0149 (19)	0.0195 (19)	−0.0121 (19)
C2	0.053 (2)	0.037 (2)	0.060 (3)	−0.0098 (19)	0.025 (2)	−0.015 (2)
C3	0.0361 (19)	0.034 (2)	0.047 (2)	−0.0079 (16)	0.0046 (17)	−0.0095 (17)
C4	0.050 (2)	0.040 (2)	0.053 (3)	−0.0133 (19)	0.019 (2)	−0.0080 (19)
C5	0.050 (2)	0.039 (2)	0.053 (3)	−0.0112 (19)	0.0221 (19)	−0.0138 (19)
C6	0.050 (2)	0.039 (3)	0.061 (3)	−0.009 (2)	0.008 (2)	−0.015 (2)
C7	0.0219 (15)	0.037 (2)	0.0360 (19)	−0.0111 (14)	−0.0002 (13)	−0.0127 (15)
C8	0.0265 (16)	0.041 (2)	0.0289 (17)	−0.0147 (15)	0.0024 (13)	−0.0117 (15)
C9	0.042 (2)	0.040 (2)	0.059 (3)	−0.0089 (18)	0.0212 (19)	−0.010 (2)
C10	0.044 (2)	0.050 (3)	0.062 (3)	−0.010 (2)	0.023 (2)	−0.018 (2)
C11	0.0343 (18)	0.042 (2)	0.041 (2)	−0.0121 (17)	0.0039 (16)	−0.0104 (17)
C12	0.046 (2)	0.045 (3)	0.049 (2)	−0.0152 (19)	0.0197 (18)	−0.0103 (19)
C13	0.044 (2)	0.043 (3)	0.054 (2)	−0.0154 (19)	0.0225 (19)	−0.016 (2)
C14	0.047 (2)	0.042 (3)	0.052 (3)	−0.0082 (19)	0.0044 (19)	−0.012 (2)
C15	0.0235 (15)	0.045 (2)	0.0342 (19)	−0.0143 (15)	0.0044 (14)	−0.0165 (16)
C16	0.0257 (16)	0.049 (2)	0.0300 (17)	−0.0160 (15)	0.0008 (13)	−0.0154 (16)
N1	0.0328 (15)	0.0385 (18)	0.0325 (16)	−0.0110 (13)	0.0060 (12)	−0.0097 (13)
N2	0.071 (3)	0.039 (2)	0.073 (3)	−0.015 (2)	0.024 (2)	−0.012 (2)
N3	0.0276 (14)	0.0423 (19)	0.0406 (17)	−0.0109 (13)	0.0074 (13)	−0.0158 (14)
N4	0.064 (3)	0.041 (2)	0.063 (3)	−0.0093 (19)	0.018 (2)	−0.0041 (19)
O1	0.0247 (12)	0.073 (2)	0.0349 (14)	−0.0166 (13)	0.0042 (10)	−0.0238 (13)
O2	0.0206 (11)	0.0637 (18)	0.0304 (13)	−0.0198 (11)	0.0010 (9)	−0.0133 (12)
O3	0.0326 (13)	0.092 (2)	0.0262 (13)	−0.0318 (14)	0.0069 (11)	−0.0220 (14)
O4	0.086 (3)	0.042 (2)	0.104 (3)	−0.0033 (18)	0.050 (2)	−0.019 (2)
O5	0.0210 (11)	0.075 (2)	0.0333 (13)	−0.0205 (12)	0.0045 (10)	−0.0192 (13)
O6	0.0283 (13)	0.083 (2)	0.0294 (13)	−0.0206 (13)	0.0020 (10)	−0.0135 (14)
O7	0.0331 (14)	0.082 (2)	0.0307 (14)	−0.0298 (14)	0.0070 (11)	−0.0227 (14)
O8	0.059 (2)	0.049 (2)	0.083 (3)	−0.0040 (16)	0.0272 (18)	−0.0146 (18)
O9	0.089 (3)	0.069 (3)	0.077 (3)	−0.032 (2)	0.034 (2)	−0.015 (2)
O10	0.108 (4)	0.102 (4)	0.096 (4)	−0.032 (3)	0.050 (3)	−0.023 (3)

Geometric parameters (Å, º)

Co1—O1	2.058 (2)	C10—C11	1.388 (6)
Co1—O2	2.128 (2)	C10—H10	0.9300
Co1—N1	2.158 (3)	C11—C12	1.379 (6)
Co2—O7	2.042 (3)	C11—C14	1.495 (6)
Co2—O5	2.141 (2)	C12—C13	1.368 (6)
Co2—N3	2.169 (3)	C12—H12	0.9300
C1—N1	1.339 (5)	C13—N3	1.337 (5)
C1—C2	1.378 (6)	C13—H13	0.9300
C1—H1	0.9300	C14—O8	1.237 (5)
C2—C3	1.377 (6)	C14—N4	1.328 (6)
C2—H2	0.9300	C15—O5	1.253 (4)
C3—C4	1.383 (6)	C15—C16	1.450 (5)
C3—C6	1.500 (6)	C16—O6	1.266 (4)
C4—C5	1.382 (6)	N2—H2A	0.89 (3)
C4—H4	0.9300	N2—H2B	0.91 (3)
C5—N1	1.333 (5)	N4—H4A	0.88 (3)
C5—H5	0.9300	N4—H4B	0.88 (3)
C6—O4	1.229 (6)	O1—H1A	0.86 (3)
C6—N2	1.321 (6)	O1—H1B	0.87 (3)
C7—O2	1.261 (4)	O7—H7A	0.86 (3)
C7—C8	1.451 (4)	O7—H7B	0.88 (3)
C8—O3	1.258 (4)	O9—H9A	0.83 (4)
C9—N3	1.339 (5)	O9—H9B	0.84 (4)
C9—C10	1.383 (6)	O10—H10A	0.87 (4)
C9—H9	0.9300	O10—H10B	0.85 (4)
O1—Co1—O2	95.67 (10)	C10—C11—C14	119.0 (4)
O1—Co1—N1	88.96 (12)	C13—C12—C11	119.6 (4)
O2—Co1—N1	88.80 (11)	C13—C12—H12	120.2
O7—Co2—O5	92.92 (10)	C11—C12—H12	120.2
O7—Co2—N3	89.31 (13)	N3—C13—C12	123.9 (4)
O5—Co2—N3	89.46 (11)	N3—C13—H13	118.1
N1—C1—C2	122.7 (4)	C12—C13—H13	118.1
N1—C1—H1	118.7	O8—C14—N4	122.2 (4)
C2—C1—H1	118.7	O8—C14—C11	119.9 (4)
C3—C2—C1	120.2 (4)	N4—C14—C11	117.9 (4)
C3—C2—H2	119.9	O5—C15—C16	137.2 (3)
C1—C2—H2	119.9	O6—C16—C15	135.7 (3)
C2—C3—C4	117.3 (4)	C5—N1—C1	117.2 (3)
C2—C3—C6	118.7 (4)	C5—N1—Co1	121.0 (3)
C4—C3—C6	124.0 (4)	C1—N1—Co1	121.8 (3)
C5—C4—C3	119.4 (4)	C6—N2—H2A	129 (4)
C5—C4—H4	120.3	C6—N2—H2B	121 (4)
C3—C4—H4	120.3	H2A—N2—H2B	111 (4)
N1—C5—C4	123.2 (4)	C13—N3—C9	117.0 (4)
N1—C5—H5	118.4	C13—N3—Co2	121.6 (3)
C4—C5—H5	118.4	C9—N3—Co2	121.4 (3)
O4—C6—N2	121.8 (4)	C14—N4—H4A	125 (4)
O4—C6—C3	119.9 (4)	C14—N4—H4B	113 (4)
N2—C6—C3	118.3 (4)	H4A—N4—H4B	108 (4)
O2—C7—C8	136.8 (3)	Co1—O1—H1A	119 (3)
O3—C8—C7	134.0 (3)	Co1—O1—H1B	123 (3)
N3—C9—C10	122.3 (4)	H1A—O1—H1B	109 (4)
N3—C9—H9	118.8	C7—O2—Co1	134.2 (2)
C10—C9—H9	118.8	C15—O5—Co2	133.2 (2)
C9—C10—C11	120.1 (4)	Co2—O7—H7A	135 (3)
C9—C10—H10	119.9	Co2—O7—H7B	112 (3)
C11—C10—H10	119.9	H7A—O7—H7B	113 (4)
C12—C11—C10	117.1 (4)	H9A—O9—H9B	109 (8)
C12—C11—C14	123.9 (4)	H10A—O10—H10B	116 (9)
N1—C1—C2—C3	−0.1 (7)	C4—C5—N1—C1	−0.5 (6)
C1—C2—C3—C4	0.0 (7)	C4—C5—N1—Co1	179.0 (3)
C1—C2—C3—C6	−178.8 (4)	C2—C1—N1—C5	0.4 (6)
C2—C3—C4—C5	−0.1 (6)	C2—C1—N1—Co1	−179.1 (3)
C6—C3—C4—C5	178.6 (4)	O1—Co1—N1—C5	58.4 (3)
C3—C4—C5—N1	0.3 (7)	O2—Co1—N1—C5	154.1 (3)
C2—C3—C6—O4	−0.4 (7)	O1—Co1—N1—C1	−122.1 (3)
C4—C3—C6—O4	−179.1 (5)	O2—Co1—N1—C1	−26.4 (3)
C2—C3—C6—N2	177.9 (5)	C12—C13—N3—C9	1.3 (6)
C4—C3—C6—N2	−0.8 (7)	C12—C13—N3—Co2	179.8 (3)
O2—C7—C8—O3	−1.7 (8)	C10—C9—N3—C13	0.2 (6)
N3—C9—C10—C11	−0.4 (7)	C10—C9—N3—Co2	−178.3 (3)
C9—C10—C11—C12	−0.7 (7)	O7—Co2—N3—C13	−151.9 (3)
C9—C10—C11—C14	179.3 (4)	O5—Co2—N3—C13	115.1 (3)
C10—C11—C12—C13	2.0 (6)	O7—Co2—N3—C9	26.5 (3)
C14—C11—C12—C13	−178.0 (4)	O5—Co2—N3—C9	−66.4 (3)
C11—C12—C13—N3	−2.4 (7)	C8—C7—O2—Co1	−1.3 (7)
C12—C11—C14—O8	−177.4 (4)	O1—Co1—O2—C7	1.4 (4)
C10—C11—C14—O8	2.7 (6)	N1—Co1—O2—C7	−87.4 (4)
C12—C11—C14—N4	3.5 (6)	C16—C15—O5—Co2	18.1 (7)
C10—C11—C14—N4	−176.4 (4)	O7—Co2—O5—C15	−1.5 (4)
O5—C15—C16—O6	2.2 (8)	N3—Co2—O5—C15	87.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3	0.86 (3)	1.80 (3)	2.635 (4)	165 (5)
O1—H1B···O6^i	0.87 (3)	1.85 (3)	2.723 (4)	174 (5)
N2—H2A···O9^ii	0.89 (3)	2.15 (3)	3.015 (6)	164 (6)
N2—H2B···O3^iii	0.91 (3)	2.35 (3)	3.214 (5)	158 (5)
N4—H4A···O10^iv	0.88 (3)	2.15 (4)	2.973 (7)	155 (6)
N4—H4B···O1^ii	0.88 (3)	2.50 (4)	3.316 (5)	155 (5)
O7—H7A···O6	0.86 (3)	1.91 (3)	2.684 (4)	149 (5)
O7—H7B···O3^v	0.88 (3)	1.75 (3)	2.613 (3)	166 (5)
O9—H9A···O8^vi	0.83 (4)	1.98 (5)	2.779 (6)	159 (8)
O9—H9B···O6^vii	0.84 (4)	2.16 (4)	2.984 (6)	170 (8)
O10—H10A···O4^ii	0.87 (4)	2.21 (9)	2.829 (7)	128 (9)
O10—H10B···O9^ii	0.85 (4)	2.24 (4)	3.083 (8)	169 (10)

Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) −x, −y, −z+1; (v) x−1, y, z−1; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z.