Aqua­nitritobis­(picolinato-κ²N,O)­cobalt(III)

The title compound, [Co(C₆H₄NO₂)₂(NO₂)(H₂O)], displays O—H...O hydrogen bonds, leading to the formation of a two-dimensional network structure. Interestingly, the oxidation and decomposition of α-pyridoin and the auto-redox reaction of cobalt nitrate occurred during the reaction process.

Key indicators

• Single-crystal X-ray study
• T = 130 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.086
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    -   N1      ..       5.08 su
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N2  -CO1 -N1  -C1    -58.10  1.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            N2  -CO1 -N1  -C5    125.30  1.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         16
            N1  -CO1 -N2  -C7   -122.60  1.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            N1  -CO1 -N2  -C11    58.40  1.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         24
            O4  -CO1 -O2  -C6     42.00  2.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         34
            O7  -CO1 -N3  -O6    179.00100.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         39
            O7  -CO1 -N3  -O5     -2.70  1.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         41
            O2  -CO1 -O4  -C12   138.00  2.00   1.555   1.555   1.555   1.555

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

   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   9 ALERT type 4 Improvement, methodology, query or suggestion


checkCIF publication errors

Alert level A
PUBL003_ALERT_1_A  The contact author's name is missing,
            _publ_contact_author_name.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick,1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Aquanitritobis(picolinato-κ²N,O)cobalt(III)

Crystal data

[Co(C6H4NO2)2(NO2)(H2O)]	F(000) = 744
Mr = 367.16	Dx = 1.866 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.065 (2) Å	Cell parameters from 4323 reflections
b = 20.736 (5) Å	θ = 2.0–27.5°
c = 7.1111 (18) Å	µ = 1.36 mm^−1
β = 102.166 (2)°	T = 130 K
V = 1306.8 (6) Å^3	Prism, red
Z = 4	0.60 × 0.40 × 0.25 mm

Data collection

Mercury CCD diffractometer	2958 independent reflections
Radiation source: fine-focus sealed tube	2785 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	h = −11→11
Tmin = 0.510, Tmax = 0.710	k = −25→26
9662 measured reflections	l = −8→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)] = 0.030	Hydrogen site location: mixed
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.5096P] where P = (Fo^2 + 2Fc^2)/3
2958 reflections	(Δ/σ)max = 0.001
214 parameters	Δρmax = 0.51 e Å^−3
2 restraints	Δρmin = −0.40 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	0.46120 (2)	0.374827 (9)	0.30460 (3)	0.01450 (10)
C1	0.66986 (17)	0.45838 (8)	0.1562 (2)	0.0206 (3)
H1	0.6149	0.4945	0.1866	0.025*
N1	0.62989 (14)	0.39881 (7)	0.19880 (18)	0.0171 (3)
O1	0.71268 (13)	0.23322 (6)	0.19207 (17)	0.0231 (3)
C2	0.79093 (18)	0.46771 (9)	0.0681 (2)	0.0249 (3)
H2	0.8192	0.5101	0.0389	0.030*
N2	0.29434 (14)	0.35250 (7)	0.41766 (19)	0.0171 (3)
O2	0.52708 (12)	0.28904 (5)	0.28134 (16)	0.0190 (2)
C3	0.87012 (18)	0.41496 (9)	0.0230 (2)	0.0271 (4)
H3	0.9522	0.4207	−0.0392	0.033*
N3	0.33770 (16)	0.36914 (6)	0.0518 (2)	0.0186 (3)
O3	0.21580 (12)	0.51898 (5)	0.41159 (17)	0.0217 (2)
C4	0.82851 (18)	0.35335 (9)	0.0696 (2)	0.0236 (3)
H4	0.8821	0.3165	0.0413	0.028*
O4	0.39643 (12)	0.46049 (5)	0.32335 (16)	0.0185 (2)
C5	0.70794 (16)	0.34721 (7)	0.1577 (2)	0.0181 (3)
O5	0.20045 (14)	0.37597 (6)	0.03040 (19)	0.0302 (3)
C6	0.64790 (17)	0.28401 (8)	0.2124 (2)	0.0187 (3)
O6	0.39520 (14)	0.35773 (8)	−0.08601 (19)	0.0348 (3)
C7	0.25334 (18)	0.29358 (8)	0.4622 (2)	0.0211 (3)
H7	0.3122	0.2573	0.4424	0.025*
O7	0.58311 (13)	0.38129 (6)	0.56823 (17)	0.0184 (2)
H7A	0.650 (2)	0.4100 (9)	0.586 (3)	0.022*
H7B	0.622 (2)	0.3445 (8)	0.622 (3)	0.022*
C8	0.12508 (18)	0.28489 (9)	0.5375 (2)	0.0240 (3)
H8	0.0960	0.2428	0.5677	0.029*
C9	0.03985 (18)	0.33767 (9)	0.5682 (2)	0.0245 (3)
H9	−0.0485	0.3321	0.6184	0.029*
C10	0.08540 (18)	0.39928 (9)	0.5244 (2)	0.0218 (3)
H10	0.0300	0.4365	0.5458	0.026*
C11	0.21333 (17)	0.40439 (7)	0.4490 (2)	0.0174 (3)
C12	0.27603 (16)	0.46694 (8)	0.3919 (2)	0.0177 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01423 (14)	0.01092 (14)	0.01922 (14)	0.00035 (7)	0.00546 (9)	−0.00020 (7)
C1	0.0193 (7)	0.0181 (8)	0.0243 (8)	−0.0014 (6)	0.0046 (6)	0.0021 (6)
N1	0.0160 (6)	0.0168 (7)	0.0190 (6)	0.0012 (5)	0.0046 (5)	−0.0001 (5)
O1	0.0231 (5)	0.0179 (6)	0.0279 (6)	0.0053 (4)	0.0043 (5)	−0.0037 (5)
C2	0.0206 (7)	0.0271 (9)	0.0269 (8)	−0.0037 (6)	0.0047 (6)	0.0067 (7)
N2	0.0160 (6)	0.0162 (6)	0.0195 (6)	−0.0013 (5)	0.0045 (5)	−0.0002 (5)
O2	0.0197 (5)	0.0136 (5)	0.0241 (6)	0.0011 (4)	0.0056 (4)	0.0000 (4)
C3	0.0168 (7)	0.0385 (10)	0.0272 (8)	−0.0005 (7)	0.0075 (6)	0.0059 (7)
N3	0.0191 (6)	0.0144 (7)	0.0222 (7)	−0.0005 (5)	0.0046 (5)	−0.0004 (5)
O3	0.0225 (5)	0.0160 (6)	0.0285 (6)	0.0033 (4)	0.0098 (4)	−0.0015 (4)
C4	0.0170 (7)	0.0294 (9)	0.0247 (8)	0.0046 (6)	0.0048 (6)	−0.0009 (7)
O4	0.0185 (5)	0.0137 (5)	0.0248 (6)	0.0003 (4)	0.0081 (4)	−0.0006 (4)
C5	0.0164 (7)	0.0181 (8)	0.0187 (7)	0.0022 (6)	0.0015 (5)	−0.0009 (6)
O5	0.0190 (6)	0.0417 (8)	0.0288 (7)	0.0051 (5)	0.0028 (5)	−0.0009 (5)
C6	0.0177 (7)	0.0185 (7)	0.0186 (7)	0.0013 (6)	0.0009 (5)	−0.0015 (6)
O6	0.0267 (6)	0.0564 (9)	0.0225 (6)	−0.0026 (6)	0.0076 (5)	−0.0066 (6)
C7	0.0219 (7)	0.0160 (7)	0.0251 (8)	−0.0002 (6)	0.0046 (6)	0.0026 (6)
O7	0.0189 (5)	0.0153 (6)	0.0207 (6)	−0.0017 (4)	0.0032 (4)	0.0002 (4)
C8	0.0233 (8)	0.0236 (8)	0.0256 (8)	−0.0075 (6)	0.0061 (6)	0.0035 (6)
C9	0.0187 (7)	0.0326 (9)	0.0234 (8)	−0.0041 (6)	0.0076 (6)	0.0026 (7)
C10	0.0190 (7)	0.0247 (9)	0.0223 (8)	0.0012 (6)	0.0058 (6)	−0.0011 (6)
C11	0.0173 (7)	0.0164 (7)	0.0187 (7)	−0.0004 (6)	0.0042 (5)	−0.0008 (6)
C12	0.0169 (7)	0.0180 (7)	0.0181 (7)	−0.0003 (6)	0.0036 (5)	−0.0009 (6)

Geometric parameters (Å, º)

Co1—O4	1.8844 (12)	N3—O6	1.2261 (19)
Co1—O2	1.8948 (12)	N3—O5	1.2294 (19)
Co1—N1	1.9071 (13)	O3—C12	1.2305 (19)
Co1—N3	1.9107 (15)	C4—C5	1.375 (2)
Co1—N2	1.9135 (13)	C4—H4	0.9500
Co1—O7	1.9700 (12)	O4—C12	1.2928 (19)
C1—N1	1.340 (2)	C5—C6	1.501 (2)
C1—C2	1.387 (2)	C7—C8	1.390 (2)
C1—H1	0.9500	C7—H7	0.9500
N1—C5	1.348 (2)	O7—H7A	0.839 (15)
O1—C6	1.229 (2)	O7—H7B	0.892 (15)
C2—C3	1.383 (3)	C8—C9	1.383 (3)
C2—H2	0.9500	C8—H8	0.9500
N2—C7	1.335 (2)	C9—C10	1.398 (3)
N2—C11	1.347 (2)	C9—H9	0.9500
O2—C6	1.295 (2)	C10—C11	1.380 (2)
C3—C4	1.392 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.506 (2)
O4—Co1—O2	178.96 (5)	O5—N3—Co1	119.10 (12)
O4—Co1—N1	94.00 (5)	C5—C4—C3	118.34 (16)
O2—Co1—N1	85.22 (5)	C5—C4—H4	120.8
O4—Co1—N3	89.73 (5)	C3—C4—H4	120.8
O2—Co1—N3	89.59 (5)	C12—O4—Co1	115.13 (10)
N1—Co1—N3	90.26 (6)	N1—C5—C4	121.93 (16)
O4—Co1—N2	84.99 (5)	N1—C5—C6	113.66 (13)
O2—Co1—N2	95.81 (5)	C4—C5—C6	124.40 (15)
N1—Co1—N2	178.17 (5)	O1—C6—O2	125.21 (15)
N3—Co1—N2	91.26 (6)	O1—C6—C5	120.62 (14)
O4—Co1—O7	89.38 (5)	O2—C6—C5	114.17 (14)
O2—Co1—O7	91.32 (5)	N2—C7—C8	120.49 (16)
N1—Co1—O7	91.26 (5)	N2—C7—H7	119.8
N3—Co1—O7	178.29 (5)	C8—C7—H7	119.8
N2—Co1—O7	87.20 (5)	Co1—O7—H7A	115.6 (14)
N1—C1—C2	120.54 (16)	Co1—O7—H7B	116.2 (13)
N1—C1—H1	119.7	H7A—O7—H7B	110 (2)
C2—C1—H1	119.7	C9—C8—C7	119.89 (16)
C1—N1—C5	120.22 (14)	C9—C8—H8	120.1
C1—N1—Co1	127.39 (11)	C7—C8—H8	120.1
C5—N1—Co1	112.30 (11)	C8—C9—C10	119.14 (15)
C3—C2—C1	119.55 (16)	C8—C9—H9	120.4
C3—C2—H2	120.2	C10—C9—H9	120.4
C1—C2—H2	120.2	C11—C10—C9	117.93 (16)
C7—N2—C11	120.20 (14)	C11—C10—H10	121.0
C7—N2—Co1	127.27 (11)	C9—C10—H10	121.0
C11—N2—Co1	112.51 (11)	N2—C11—C10	122.32 (15)
C6—O2—Co1	114.58 (10)	N2—C11—C12	113.17 (13)
C2—C3—C4	119.41 (15)	C10—C11—C12	124.51 (14)
C2—C3—H3	120.3	O3—C12—O4	124.32 (15)
C4—C3—H3	120.3	O3—C12—C11	121.53 (13)
O6—N3—O5	120.86 (15)	O4—C12—C11	114.15 (13)
O6—N3—Co1	120.03 (11)
C2—C1—N1—C5	0.5 (2)	N2—Co1—N3—O5	23.70 (12)
C2—C1—N1—Co1	−175.85 (12)	O7—Co1—N3—O5	−2.7 (17)
O4—Co1—N1—C1	−1.61 (14)	C2—C3—C4—C5	0.7 (2)
O2—Co1—N1—C1	177.71 (14)	O2—Co1—O4—C12	138 (2)
N3—Co1—N1—C1	88.14 (14)	N1—Co1—O4—C12	179.57 (11)
N2—Co1—N1—C1	−58.1 (17)	N3—Co1—O4—C12	89.33 (11)
O7—Co1—N1—C1	−91.08 (14)	N2—Co1—O4—C12	−1.96 (11)
O4—Co1—N1—C5	−178.24 (10)	O7—Co1—O4—C12	−89.21 (11)
O2—Co1—N1—C5	1.07 (10)	C1—N1—C5—C4	−0.9 (2)
N3—Co1—N1—C5	−88.49 (11)	Co1—N1—C5—C4	176.05 (12)
N2—Co1—N1—C5	125.3 (17)	C1—N1—C5—C6	−179.35 (13)
O7—Co1—N1—C5	92.29 (11)	Co1—N1—C5—C6	−2.45 (16)
N1—C1—C2—C3	0.4 (3)	C3—C4—C5—N1	0.2 (2)
O4—Co1—N2—C7	−179.22 (14)	C3—C4—C5—C6	178.55 (14)
O2—Co1—N2—C7	1.45 (14)	Co1—O2—C6—O1	177.20 (12)
N1—Co1—N2—C7	−122.6 (17)	Co1—O2—C6—C5	−2.21 (16)
N3—Co1—N2—C7	91.17 (14)	N1—C5—C6—O1	−176.32 (14)
O7—Co1—N2—C7	−89.59 (14)	C4—C5—C6—O1	5.2 (2)
O4—Co1—N2—C11	1.80 (10)	N1—C5—C6—O2	3.12 (19)
O2—Co1—N2—C11	−177.53 (10)	C4—C5—C6—O2	−175.33 (14)
N1—Co1—N2—C11	58.4 (17)	C11—N2—C7—C8	1.4 (2)
N3—Co1—N2—C11	−87.81 (11)	Co1—N2—C7—C8	−177.53 (12)
O7—Co1—N2—C11	91.43 (11)	N2—C7—C8—C9	−0.6 (3)
O4—Co1—O2—C6	42 (2)	C7—C8—C9—C10	−0.6 (2)
N1—Co1—O2—C6	0.73 (11)	C8—C9—C10—C11	1.0 (2)
N3—Co1—O2—C6	91.03 (11)	C7—N2—C11—C10	−1.0 (2)
N2—Co1—O2—C6	−177.74 (11)	Co1—N2—C11—C10	178.09 (12)
O7—Co1—O2—C6	−90.42 (11)	C7—N2—C11—C12	179.57 (14)
C1—C2—C3—C4	−1.0 (3)	Co1—N2—C11—C12	−1.37 (16)
O4—Co1—N3—O6	119.94 (13)	C9—C10—C11—N2	−0.2 (2)
O2—Co1—N3—O6	−59.28 (13)	C9—C10—C11—C12	179.16 (14)
N1—Co1—N3—O6	25.94 (14)	Co1—O4—C12—O3	−178.72 (12)
N2—Co1—N3—O6	−155.08 (14)	Co1—O4—C12—C11	1.66 (16)
O7—Co1—N3—O6	179 (100)	N2—C11—C12—O3	−179.79 (14)
O4—Co1—N3—O5	−61.28 (12)	C10—C11—C12—O3	0.8 (2)
O2—Co1—N3—O5	119.50 (12)	N2—C11—C12—O4	−0.16 (19)
N1—Co1—N3—O5	−155.28 (12)	C10—C11—C12—O4	−179.60 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3^i	0.84 (2)	1.91 (2)	2.7405 (17)	171 (2)
O7—H7B···O1^ii	0.89 (2)	1.83 (2)	2.7124 (17)	170 (2)

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