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The title compound, [Cu(C7H8N2O)2(H2O)2](NO3)2, was prepared by the reaction of 2-cyano-3-methyl­pyridine with Cu(NO3)2·3H2O in a methanol/water solution. In the crystal structure, the CuII ion is located on an inversion centre and is coordinated by two 3-methyl­pyridine-2-carboxamide ligands in the equatorial plane and two water mol­ecules in the axial positions, forming an elongated octa­hedral coordination geometry. The Cu—Oaxial bond distance of 2.4715 (18) Å is much longer than the Cu—Oequatorial bond distance of 1.9471 (17) Å, showing a Jahn–Teller distortion. The nitrate anions are linked with the CuII complex cation via O—H...O hydrogen bonding.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027109/xu2256sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027109/xu2256Isup2.hkl
Contains datablock I

CCDC reference: 654731

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.033
  • wR factor = 0.092
  • Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.39 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O1 .. 6.75 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O5 .. 6.18 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N1 .. 6.41 su PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N3
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 Cu1 (2) 2.34
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 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 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

The title compound is shown in Fig. 1. The pyridine ring, methyl and amide substituent groups are almost coplanar, and their bond lengths and angles are normal. The CuII atom is coordinated by two N and two O atoms in the equatorial plane, and two O atoms at the apical positions of elongated octahedron (Table 1). The nitrate ion does not connect CuII atom directly but likes with the CuII complex cation via O—H···O hydrogen bonding (Table 2).

Further analysis of the short contacts present in (I) shows that there are O5—H5B···O2, O5—H5B···O4, O5—H5A···O3ii, O5—H5A···O2ii, [symmetry code: (ii)-x + 1/2,+y - 1/2,-z + 1/2 + 1], N2—H2A···O2iii, and N2—H2B···O5iii [symmetry code:(iii)-x + 1,-y + 1,-z + 1] interactions. All these contacts can be regarded as hydrogen bonds, which hold the complex cations and nitrate anions together.

Related literature top

For related structures, see: Pestov et al. (2005); Xuan et al. (2003).

Experimental top

A methanol solution (5 ml) of 2-cyano-3-methylpyridine (0.2368 g, 0.20 mmol) was mixed with an aqueous solution (5 ml) of Cu(NO3)2.3H2O (0.0491, 0.20 mmol) in a round-bottomed flask. The solution was refluxed for 10 min and then cooled to room temperature. Single crystals of the title compound were obtained after 5 d.

Refinement top

The H atoms bonded to N2 and O5 were founded in a difference Fourier map and refined as riding in their as-found relative positions with Uiso(H) = 1.5Ueq(O,N). Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angle was refined to fit the electron density, Uiso(H) = 1.5Ueq(C). Aromatic H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Structure description top

The title compound is shown in Fig. 1. The pyridine ring, methyl and amide substituent groups are almost coplanar, and their bond lengths and angles are normal. The CuII atom is coordinated by two N and two O atoms in the equatorial plane, and two O atoms at the apical positions of elongated octahedron (Table 1). The nitrate ion does not connect CuII atom directly but likes with the CuII complex cation via O—H···O hydrogen bonding (Table 2).

Further analysis of the short contacts present in (I) shows that there are O5—H5B···O2, O5—H5B···O4, O5—H5A···O3ii, O5—H5A···O2ii, [symmetry code: (ii)-x + 1/2,+y - 1/2,-z + 1/2 + 1], N2—H2A···O2iii, and N2—H2B···O5iii [symmetry code:(iii)-x + 1,-y + 1,-z + 1] interactions. All these contacts can be regarded as hydrogen bonds, which hold the complex cations and nitrate anions together.

For related structures, see: Pestov et al. (2005); Xuan et al. (2003).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability lever and H atoms are shown as small spheres of arbitrary radii.
Diaquabis(3-methylpyridine-2-carboxamide-κ2N,O)copper(II) dinitrate top
Crystal data top
[Cu(C7H8N2O)2(H2O)2](NO3)2F(000) = 510
Mr = 495.9Dx = 1.683 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7644 reflections
a = 6.656 (4) Åθ = 3.2–27.0°
b = 11.874 (9) ŵ = 1.19 mm1
c = 12.472 (6) ÅT = 293 K
β = 96.97 (2)°Prism, blue
V = 978.4 (10) Å30.20 × 0.14 × 0.10 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2221 independent reflections
Radiation source: fine-focus sealed tube1853 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 3.3°
ω scansh = 87
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1515
Tmin = 0.840, Tmax = 0.885l = 1416
9362 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0509P)2 + 0.2656P]
where P = (Fo2 + 2Fc2)/3
2221 reflections(Δ/σ)max < 0.001
143 parametersΔρmax = 0.61 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
[Cu(C7H8N2O)2(H2O)2](NO3)2V = 978.4 (10) Å3
Mr = 495.9Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.656 (4) ŵ = 1.19 mm1
b = 11.874 (9) ÅT = 293 K
c = 12.472 (6) Å0.20 × 0.14 × 0.10 mm
β = 96.97 (2)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2221 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1853 reflections with I > 2σ(I)
Tmin = 0.840, Tmax = 0.885Rint = 0.026
9362 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.09Δρmax = 0.61 e Å3
2221 reflectionsΔρmin = 0.26 e Å3
143 parameters
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
xyzUiso*/Ueq
Cu10.00000.50000.50000.03437 (13)
N10.0100 (2)0.33946 (13)0.46298 (13)0.0350 (3)
N20.4421 (3)0.38605 (17)0.34147 (17)0.0527 (5)
N30.1397 (3)0.67879 (16)0.84496 (14)0.0448 (4)
O10.2432 (2)0.49394 (11)0.42776 (14)0.0445 (4)
O20.2770 (3)0.71509 (18)0.79573 (17)0.0717 (5)
H2A0.46940.32640.31060.108*
H2B0.53520.44710.34500.108*
O30.0465 (3)0.74715 (19)0.89250 (18)0.0798 (6)
O40.0982 (5)0.57935 (18)0.8442 (2)0.1048 (9)
O50.2239 (2)0.46062 (14)0.66877 (12)0.0495 (4)
H5A0.24080.39240.67740.074*
H5B0.18960.49270.72310.074*
C10.1385 (3)0.30383 (16)0.40762 (14)0.0344 (4)
C20.1543 (3)0.19255 (17)0.37466 (16)0.0415 (5)
C30.0070 (4)0.11950 (18)0.40420 (19)0.0513 (6)
H30.01050.04420.38420.062*
C40.1453 (4)0.15636 (18)0.46297 (19)0.0499 (5)
H40.24270.10710.48300.060*
C50.1461 (3)0.26862 (17)0.49020 (16)0.0408 (4)
H50.24680.29520.52930.049*
C60.3131 (4)0.1473 (2)0.3118 (3)0.0694 (8)
H6A0.28270.07040.29250.104*
H6B0.44260.15120.35490.104*
H6C0.31630.19130.24740.104*
C70.2820 (3)0.40018 (17)0.39072 (15)0.0366 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0337 (2)0.02471 (18)0.0487 (2)0.00089 (12)0.02154 (14)0.00463 (12)
N10.0358 (9)0.0301 (8)0.0401 (8)0.0013 (6)0.0092 (6)0.0021 (6)
N20.0418 (10)0.0568 (11)0.0642 (12)0.0062 (9)0.0262 (9)0.0048 (9)
N30.0458 (10)0.0465 (11)0.0425 (9)0.0032 (8)0.0074 (8)0.0063 (7)
O10.0420 (8)0.0365 (8)0.0597 (9)0.0018 (6)0.0257 (7)0.0037 (6)
O20.0623 (11)0.0767 (13)0.0827 (13)0.0073 (10)0.0361 (10)0.0132 (10)
O30.0647 (12)0.0893 (15)0.0897 (14)0.0180 (11)0.0272 (10)0.0272 (11)
O40.166 (3)0.0532 (13)0.1063 (18)0.0334 (14)0.0600 (18)0.0137 (11)
O50.0574 (10)0.0401 (8)0.0512 (9)0.0044 (7)0.0076 (7)0.0009 (7)
C10.0331 (9)0.0347 (10)0.0347 (9)0.0086 (7)0.0006 (7)0.0046 (7)
C20.0424 (11)0.0361 (11)0.0436 (10)0.0110 (8)0.0048 (8)0.0084 (8)
C30.0623 (15)0.0307 (10)0.0570 (13)0.0035 (10)0.0085 (11)0.0053 (9)
C40.0535 (13)0.0361 (11)0.0573 (12)0.0113 (9)0.0045 (10)0.0086 (9)
C50.0435 (11)0.0367 (11)0.0427 (10)0.0017 (8)0.0079 (8)0.0028 (8)
C60.0615 (16)0.0604 (17)0.0868 (19)0.0161 (13)0.0112 (14)0.0331 (14)
C70.0343 (10)0.0385 (10)0.0380 (9)0.0075 (8)0.0084 (8)0.0016 (7)
Geometric parameters (Å, º) top
Cu1—O11.9471 (17)O5—H5A0.8237
Cu1—O1i1.9471 (17)O5—H5B0.8332
Cu1—O52.4715 (18)C1—C21.392 (3)
Cu1—O5i2.4715 (18)C1—C71.521 (3)
Cu1—N11.961 (2)C2—C31.392 (3)
Cu1—N1i1.961 (2)C2—C61.490 (3)
N1—C51.311 (3)C3—C41.392 (4)
N1—C11.341 (2)C3—H30.9300
N2—C71.304 (3)C4—C51.376 (3)
N2—H2A0.8365C4—H40.9300
N2—H2B0.9519C5—H50.9300
N3—O41.213 (3)C6—H6A0.9600
N3—O31.218 (2)C6—H6B0.9600
N3—O21.239 (2)C6—H6C0.9600
O1—C71.244 (2)
O1—Cu1—O1i180.0C1—C2—C6125.6 (2)
O1—Cu1—N182.04 (6)C3—C2—C6118.8 (2)
O1i—Cu1—N197.96 (6)C4—C3—C2121.7 (2)
O1—Cu1—N1i97.96 (6)C4—C3—H3119.2
O1i—Cu1—N1i82.04 (6)C2—C3—H3119.2
N1—Cu1—N1i180.0C5—C4—C3117.4 (2)
C5—N1—C1120.44 (18)C5—C4—H4121.3
C5—N1—Cu1124.59 (14)C3—C4—H4121.3
C1—N1—Cu1114.95 (13)N1—C5—C4122.3 (2)
C7—N2—H2A124.2N1—C5—H5118.9
C7—N2—H2B116.4C4—C5—H5118.9
H2A—N2—H2B119.3C2—C6—H6A109.5
O4—N3—O3121.6 (2)C2—C6—H6B109.5
O4—N3—O2121.1 (2)H6A—C6—H6B109.5
O3—N3—O2117.3 (2)C2—C6—H6C109.5
C7—O1—Cu1115.23 (13)H6A—C6—H6C109.5
H5A—O5—H5B112.9H6B—C6—H6C109.5
N1—C1—C2122.58 (19)O1—C7—N2120.5 (2)
N1—C1—C7110.39 (16)O1—C7—C1117.36 (17)
C2—C1—C7127.01 (18)N2—C7—C1122.08 (18)
C1—C2—C3115.63 (19)
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O2ii0.842.322.940 (4)131
N2—H2B···O5ii0.951.972.886 (3)163
O5—H5A···O2iii0.822.142.949 (4)169
O5—H5A···O3iii0.822.463.103 (4)136
O5—H5B···O40.831.982.814 (4)175
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x+1/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[Cu(C7H8N2O)2(H2O)2](NO3)2
Mr495.9
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.656 (4), 11.874 (9), 12.472 (6)
β (°) 96.97 (2)
V3)978.4 (10)
Z2
Radiation typeMo Kα
µ (mm1)1.19
Crystal size (mm)0.20 × 0.14 × 0.10
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.840, 0.885
No. of measured, independent and
observed [I > 2σ(I)] reflections
9362, 2221, 1853
Rint0.026
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.092, 1.09
No. of reflections2221
No. of parameters143
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.61, 0.26

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top
Cu1—O11.9471 (17)Cu1—N11.961 (2)
Cu1—O52.4715 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O2i0.842.322.940 (4)131
N2—H2B···O5i0.951.972.886 (3)163
O5—H5A···O2ii0.822.142.949 (4)169
O5—H5A···O3ii0.822.463.103 (4)136
O5—H5B···O40.831.982.814 (4)175
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y1/2, z+3/2.
 

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