By the hydrothermal method, a four-coordinate monomeric Co
II complex with two isonicotinate (C
6H
4NO
2) ligands, [Co(
L)
2(H
2O)
2]·2H
2O, where H
L 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 CoN
2O
2 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.
Supporting information
CCDC reference: 231836
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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
top
Crystal data top
[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) Å3 | 0.30 × 0.25 × 0.20 mm |
Data collection top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0591P)2 + 0.5683P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.122 (14) |
Special details top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
Co1—O3i | 1.989 (3) | C5—H5A | 0.930 |
Co1—O3 | 1.989 (3) | C2—C3 | 1.387 (6) |
Co1—N1i | 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) | | |
| | | |
O3i—Co1—O3 | 180.0 | N1—C5—H5A | 118.8 |
O3i—Co1—N1i | 90.22 (12) | C4—C5—H5A | 118.8 |
O3—Co1—N1i | 89.78 (12) | C1—C2—C3 | 119.7 (4) |
O3i—Co1—N1 | 89.78 (12) | C1—C2—H2A | 120.2 |
O3—Co1—N1 | 90.22 (12) | C3—C2—H2A | 120.2 |
N1i—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) | | |
| | | |
O3i—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) |
O3i—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2ii | 0.83 (1) | 1.91 (2) | 2.730 (4) | 169 (6) |
O3—H3B···O1iii | 0.83 (1) | 1.80 (2) | 2.621 (4) | 169 (6) |
O1W—H1WA···O1iv | 0.83 (1) | 2.01 (2) | 2.828 (5) | 169 (6) |
O1W—H1WB···O2iii | 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. |