trans-Di­aqua­bis­(pyridine-4-carboxyl­ato)­cobalt(II) dihydrate

By the hydro­thermal method, a four-coordinate monomeric Co^II complex with two isonicotinate (C₆H₄NO₂) ligands, [Co(L)₂(H₂O)₂]·2H₂O, where HL is isonicotinic acid, has been synthesized; it has been characterized by elemental analysis and X-ray diffraction techniques. The crystal structure reveals that the Co^II atom, on an inversion center, has a CoN₂O₂ square-planar primary coordination environment and weak axial interactions with two more water mol­ecules. Isonicotinate is bonded through nitro­gen. A striking structural feature is the formation of a three-dimensional supramol­ecular architecture through intermolecular O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.044
• wR factor = 0.114
• Data-to-parameter ratio = 9.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.83(5), Rep   0.827(10) ......       5.00 su-Rat
              O3   -H3B     1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.83(5), Rep   0.825(11) ......       4.55 su-Rat
              O1W  -H1WA    1.555   1.555
PLAT731_ALERT_1_B Bond    Calc     0.82(8), Rep   0.824(10) ......       8.00 su-Rat
              O1W  -H1WB    1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.83(5), Rep   0.827(10) ......       5.00 su-Rat
              O3   -H3B     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.83(5), Rep   0.825(11) ......       4.55 su-Rat
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.82(8), Rep   0.824(10) ......       8.00 su-Rat
              O1W  -H2#     1.555   1.555
PLAT736_ALERT_1_B H...A   Calc     2.14(8), Rep   2.141(18) ......       4.44 su-Rat
              H2#  -O2      1.555   2.676

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.89
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    -   N1       =       7.85 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2
PLAT731_ALERT_1_C Bond    Calc     0.82(4), Rep   0.825(11) ......       3.64 su-Rat
              O3   -H3A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(4), Rep   0.825(11) ......       3.64 su-Rat
              O3   -H3A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.92(4), Rep   1.914(16) ......       2.50 su-Rat
              H3A  -O2      1.555   1.666
PLAT736_ALERT_1_C H...A   Calc     1.80(5), Rep   1.804(16) ......       3.12 su-Rat
              H3B  -O1      1.555   2.676
PLAT736_ALERT_1_C H...A   Calc     2.01(5), Rep   2.014(17) ......       2.94 su-Rat
              H1#  -O1      1.555   2.776
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

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

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

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Computing details

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

trans-Diaquabis(pyridine-4-carboxylato)cobalt(II) dihydrate

Crystal data

[Co(C6H4NO2)2(H2O)2]·2H2O	Z = 1
Mr = 375.20	F(000) = 193
Triclinic, P1	Dx = 1.760 Mg m^−3
a = 6.3367 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.8936 (9) Å	Cell parameters from 642 reflections
c = 9.1801 (12) Å	θ = 3.2–23.0°
α = 99.396 (2)°	µ = 1.26 mm^−1
β = 105.286 (2)°	T = 293 K
γ = 108.178 (2)°	Block, red
V = 354.09 (8) Å^3	0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1217 independent reflections
Radiation source: fine-focus sealed tube	1118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 25.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.711, Tmax = 0.777	k = −5→8
1810 measured reflections	l = −10→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 0.5683P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
1217 reflections	Δρmax = 0.47 e Å^−3
123 parameters	Δρmin = −0.52 e Å^−3
4 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.122 (14)

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	1.0000	1.0000	1.0000	0.0266 (3)
O3	0.8465 (5)	1.2048 (5)	1.0410 (3)	0.0366 (7)
N1	0.7675 (6)	0.8741 (5)	0.7811 (4)	0.0328 (7)
C1	0.8451 (7)	0.8721 (6)	0.6588 (4)	0.0347 (9)
H1A	1.0068	0.9196	0.6778	0.042*
C5	0.5340 (7)	0.7990 (7)	0.7521 (4)	0.0362 (9)
H5A	0.4784	0.7979	0.8363	0.043*
C2	0.6948 (7)	0.8024 (6)	0.5060 (4)	0.0343 (9)
H2A	0.7551	0.8052	0.4240	0.041*
O2	0.0703 (5)	0.5619 (5)	0.2856 (3)	0.0486 (8)
O1	0.3730 (6)	0.7019 (5)	0.2062 (3)	0.0482 (8)
C3	0.4529 (7)	0.7280 (6)	0.4749 (4)	0.0303 (8)
C6	0.2835 (7)	0.6569 (6)	0.3088 (5)	0.0355 (9)
C4	0.3727 (7)	0.7230 (6)	0.6016 (4)	0.0355 (9)
H4A	0.2118	0.6690	0.5855	0.043*
H3A	0.929 (10)	1.315 (6)	1.111 (5)	0.08 (2)*
H3B	0.793 (10)	1.250 (9)	0.967 (5)	0.075 (19)*
O1W	1.2453 (6)	1.2675 (6)	0.9053 (4)	0.0515 (8)
H1WA	1.368 (6)	1.289 (10)	0.884 (7)	0.08 (2)*
H1WB	1.171 (13)	1.327 (12)	0.854 (8)	0.12 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0243 (4)	0.0362 (5)	0.0146 (4)	0.0120 (3)	0.0009 (3)	0.0026 (3)
O3	0.0373 (16)	0.0447 (17)	0.0251 (14)	0.0184 (14)	0.0040 (12)	0.0065 (13)
N1	0.0325 (17)	0.0378 (17)	0.0269 (16)	0.0137 (14)	0.0076 (13)	0.0088 (13)
C1	0.0291 (19)	0.043 (2)	0.032 (2)	0.0131 (17)	0.0102 (16)	0.0100 (16)
C5	0.033 (2)	0.048 (2)	0.0277 (19)	0.0142 (18)	0.0111 (16)	0.0085 (17)
C2	0.034 (2)	0.041 (2)	0.0244 (18)	0.0099 (17)	0.0079 (16)	0.0088 (16)
O2	0.0335 (17)	0.0586 (19)	0.0350 (16)	0.0053 (14)	0.0006 (13)	0.0053 (14)
O1	0.0469 (17)	0.072 (2)	0.0273 (15)	0.0259 (16)	0.0092 (13)	0.0165 (14)
C3	0.037 (2)	0.0274 (18)	0.0256 (18)	0.0134 (16)	0.0073 (16)	0.0060 (14)
C6	0.039 (2)	0.036 (2)	0.0278 (19)	0.0172 (18)	0.0048 (17)	0.0059 (15)
C4	0.0275 (19)	0.040 (2)	0.030 (2)	0.0077 (16)	0.0039 (16)	0.0055 (16)
O1W	0.0419 (19)	0.062 (2)	0.051 (2)	0.0158 (17)	0.0177 (16)	0.0208 (17)

Geometric parameters (Å, º)

Co1—O3^i	1.989 (3)	C5—H5A	0.930
Co1—O3	1.989 (3)	C2—C3	1.387 (6)
Co1—N1^i	2.008 (3)	C2—H2A	0.930
Co1—N1	2.008 (3)	O2—C6	1.245 (5)
O3—H3A	0.825 (11)	O1—C6	1.255 (5)
O3—H3B	0.827 (10)	C3—C4	1.389 (6)
N1—C1	1.339 (5)	C3—C6	1.511 (5)
N1—C5	1.341 (5)	C4—H4A	0.930
C1—C2	1.377 (5)	O1W—H1WA	0.825 (11)
C1—H1A	0.930	O1W—H1WB	0.824 (10)
C5—C4	1.383 (5)
O3^i—Co1—O3	180.0	N1—C5—H5A	118.8
O3^i—Co1—N1^i	90.22 (12)	C4—C5—H5A	118.8
O3—Co1—N1^i	89.78 (12)	C1—C2—C3	119.7 (4)
O3^i—Co1—N1	89.78 (12)	C1—C2—H2A	120.2
O3—Co1—N1	90.22 (12)	C3—C2—H2A	120.2
N1^i—Co1—N1	180.0	C2—C3—C4	117.7 (3)
Co1—O3—H3A	116 (5)	C2—C3—C6	121.0 (3)
Co1—O3—H3B	117 (4)	C4—C3—C6	121.3 (3)
H3A—O3—H3B	102 (6)	O2—C6—O1	125.9 (4)
C1—N1—C5	118.2 (3)	O2—C6—C3	118.2 (4)
C1—N1—Co1	119.7 (3)	O1—C6—C3	115.9 (4)
C5—N1—Co1	122.1 (3)	C5—C4—C3	119.4 (4)
N1—C1—C2	122.5 (4)	C5—C4—H4A	120.3
N1—C1—H1A	118.7	C3—C4—H4A	120.3
C2—C1—H1A	118.7	H1WA—O1W—H1WB	107 (7)
N1—C5—C4	122.4 (4)
O3^i—Co1—N1—C1	−58.4 (3)	C1—C2—C3—C4	−1.4 (6)
O3—Co1—N1—C1	121.6 (3)	C1—C2—C3—C6	178.1 (3)
O3^i—Co1—N1—C5	124.5 (3)	C2—C3—C6—O2	169.2 (4)
O3—Co1—N1—C5	−55.5 (3)	C4—C3—C6—O2	−11.4 (6)
C5—N1—C1—C2	2.1 (6)	C2—C3—C6—O1	−11.4 (6)
Co1—N1—C1—C2	−175.2 (3)	C4—C3—C6—O1	168.0 (4)
C1—N1—C5—C4	−0.9 (6)	N1—C5—C4—C3	−1.4 (6)
Co1—N1—C5—C4	176.3 (3)	C2—C3—C4—C5	2.5 (6)
N1—C1—C2—C3	−0.9 (6)	C6—C3—C4—C5	−176.9 (4)

Symmetry code: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^ii	0.83 (1)	1.91 (2)	2.730 (4)	169 (6)
O3—H3B···O1^iii	0.83 (1)	1.80 (2)	2.621 (4)	169 (6)
O1W—H1WA···O1^iv	0.83 (1)	2.01 (2)	2.828 (5)	169 (6)
O1W—H1WB···O2^iii	0.82 (1)	2.14 (2)	2.957 (5)	171 (8)

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