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The title compound, [Cu(C6H6N2O)2(H2O)2](C4O4) [or Cu(pia)2(H2O)2.Sq, where pia is picolin­amide or pyridine-2-carboxy­amide, and Sq is the squarate dianion, (C4O4)2−], has been synthesized and the crystal structure determination is reported. The Cu2+ cation, located on a centre of symmetry, is coordinated by two symmetry-related aqua ligands together with a pair of symmetry-related bidentate pia mol­ecules and exhibits elongated octahedral trans-[CuN2O4] coordination geometry. The unligated Sq dianion also lies on a crystallographic inversion centre. The squarate O atoms link the Sq ions to the metal complex via O—H...O and O—H...N hydrogen bonds. Intermolecular π–π and C—H...π interactions between the moieties also stabilize the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804030090/ci6487sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536804030090/ci6487Isup2.hkl
Contains datablock I

CCDC reference: 259075

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.025
  • wR factor = 0.072
  • Data-to-parameter ratio = 15.8

checkCIF/PLATON results

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Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O1 .. 7.15 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O2 .. 9.07 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - N2 .. 6.68 su PLAT480_ALERT_4_C Long H...A H-Bond Reported H6 .. CG1 .. 3.13 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Diaquabis(pyridine-2-carboxamide-κ2N1,O2)copper(II) squarate top
Crystal data top
[Cu(C6H6N2O)2(H2O)2](C4O4)Z = 1
Mr = 455.87F(000) = 233
Triclinic, P1Dx = 1.784 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1240 (9) ÅCell parameters from 13950 reflections
b = 7.7627 (9) Åθ = 2.7–29.7°
c = 8.1191 (9) ŵ = 1.35 mm1
α = 108.150 (9)°T = 293 K
β = 92.225 (10)°Prism, green
γ = 94.531 (10)°0.42 × 0.27 × 0.18 mm
V = 424.37 (9) Å3
Data collection top
Stoe IPDS-2
diffractometer
2361 independent reflections
Radiation source: fine-focus sealed tube2241 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.070
Detector resolution: 6.67 pixels mm-1θmax = 29.6°, θmin = 2.7°
ω scansh = 99
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
k = 1010
Tmin = 0.656, Tmax = 0.803l = 1111
8483 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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0346P)2 + 0.1621P]
where P = (Fo2 + 2Fc2)/3
2361 reflections(Δ/σ)max < 0.001
149 parametersΔρmax = 0.40 e Å3
4 restraintsΔρmin = 0.34 e Å3
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
C10.21475 (19)0.32463 (17)1.14790 (17)0.0270 (2)
C20.16763 (18)0.32436 (16)0.96700 (17)0.0244 (2)
C30.2272 (2)0.45950 (18)0.89902 (19)0.0313 (3)
H30.30450.56140.96600.038*
C40.1698 (2)0.4407 (2)0.7288 (2)0.0369 (3)
H40.20880.52980.67960.044*
C50.0547 (3)0.2889 (2)0.6333 (2)0.0379 (3)
H50.01440.27400.51890.045*
C60.0003 (2)0.1586 (2)0.71037 (19)0.0330 (3)
H60.07880.05620.64630.040*
C70.47741 (19)0.08788 (17)0.37386 (17)0.0262 (2)
C80.5383 (2)0.10690 (17)0.45315 (17)0.0276 (3)
N10.3271 (2)0.45972 (18)1.25195 (18)0.0374 (3)
N20.05588 (17)0.17558 (15)0.87345 (15)0.0264 (2)
O10.14535 (16)0.19543 (14)1.19395 (13)0.0343 (2)
O20.29209 (19)0.11154 (19)0.93404 (17)0.0439 (3)
O30.44753 (17)0.19531 (14)0.22224 (13)0.0354 (2)
O40.58527 (19)0.23626 (15)0.39787 (15)0.0420 (3)
Cu10.00000.00001.00000.02944 (9)
H1A0.366 (3)0.556 (2)1.228 (3)0.046 (6)*
H1B0.356 (4)0.454 (4)1.353 (2)0.064 (7)*
H2A0.345 (4)0.132 (4)0.845 (3)0.059 (7)*
H2B0.359 (3)0.118 (3)1.016 (2)0.045 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0309 (6)0.0227 (5)0.0258 (6)0.0030 (5)0.0004 (5)0.0068 (5)
C20.0275 (6)0.0196 (5)0.0258 (6)0.0009 (4)0.0030 (4)0.0074 (4)
C30.0371 (7)0.0229 (6)0.0343 (7)0.0047 (5)0.0028 (5)0.0113 (5)
C40.0496 (8)0.0296 (7)0.0359 (7)0.0019 (6)0.0052 (6)0.0179 (6)
C50.0525 (9)0.0352 (7)0.0282 (7)0.0004 (6)0.0007 (6)0.0146 (6)
C60.0423 (7)0.0285 (6)0.0257 (6)0.0052 (5)0.0014 (5)0.0077 (5)
C70.0318 (6)0.0226 (5)0.0235 (6)0.0032 (4)0.0015 (5)0.0080 (5)
C80.0353 (6)0.0235 (6)0.0235 (6)0.0046 (5)0.0020 (5)0.0091 (5)
N10.0467 (7)0.0308 (6)0.0312 (6)0.0141 (5)0.0086 (5)0.0104 (5)
N20.0328 (5)0.0213 (5)0.0243 (5)0.0042 (4)0.0018 (4)0.0078 (4)
O10.0465 (6)0.0289 (5)0.0263 (5)0.0127 (4)0.0031 (4)0.0113 (4)
O20.0471 (7)0.0563 (7)0.0341 (6)0.0098 (6)0.0054 (5)0.0211 (6)
O30.0519 (6)0.0274 (5)0.0225 (5)0.0062 (4)0.0023 (4)0.0046 (4)
O40.0668 (8)0.0289 (5)0.0309 (5)0.0125 (5)0.0020 (5)0.0151 (4)
Cu10.04224 (15)0.02166 (12)0.02307 (12)0.01158 (9)0.00145 (9)0.00909 (8)
Geometric parameters (Å, º) top
C1—O11.2489 (16)C6—H60.93
C1—N11.3104 (18)C7—O31.2523 (16)
C1—C21.4932 (19)C7—C81.4687 (17)
C2—N21.3438 (16)C8—O41.2495 (16)
C2—C31.3762 (18)N1—H1A0.855 (16)
C3—C41.385 (2)N1—H1B0.851 (17)
C3—H30.93N2—Cu11.9724 (11)
C4—C51.375 (2)O1—Cu11.9976 (10)
C4—H40.93O2—Cu12.3342 (14)
C5—C61.385 (2)O2—H2A0.807 (17)
C5—H50.93O2—H2B0.816 (16)
C6—N21.3314 (18)
O1—C1—N1122.56 (13)C5—C6—H6119.0
O1—C1—C2118.50 (11)O3—C7—C8135.81 (13)
N1—C1—C2118.94 (12)O4—C8—C7135.52 (13)
N2—C2—C3122.03 (12)C1—N1—H1A124.5 (15)
N2—C2—C1112.57 (11)C1—N1—H1B117.3 (18)
C3—C2—C1125.40 (12)H1A—N1—H1B118 (2)
C2—C3—C4118.68 (13)C6—N2—C2119.16 (12)
C2—C3—H3120.7C6—N2—Cu1127.34 (9)
C4—C3—H3120.7C2—N2—Cu1113.48 (9)
C5—C4—C3119.31 (13)C1—O1—Cu1112.95 (9)
C5—C4—H4120.3Cu1—O2—H2A129.6 (19)
C3—C4—H4120.3Cu1—O2—H2B116.4 (16)
C4—C5—C6118.86 (14)H2A—O2—H2B113 (3)
C4—C5—H5120.6N2—Cu1—O182.17 (4)
C6—C5—H5120.6N2—Cu1—O289.46 (5)
N2—C6—C5121.96 (13)O1—Cu1—O285.19 (5)
N2—C6—H6119.0
O1—C1—C2—N21.74 (19)C3—C2—N2—C60.5 (2)
N1—C1—C2—N2178.17 (13)C1—C2—N2—C6178.82 (12)
O1—C1—C2—C3177.57 (13)C3—C2—N2—Cu1177.84 (11)
N1—C1—C2—C32.5 (2)C1—C2—N2—Cu12.83 (14)
N2—C2—C3—C40.0 (2)N1—C1—O1—Cu1174.61 (12)
C1—C2—C3—C4179.29 (14)C2—C1—O1—Cu15.30 (16)
C2—C3—C4—C50.4 (2)C6—N2—Cu1—O1177.49 (14)
C3—C4—C5—C60.2 (3)C2—N2—Cu1—O14.32 (10)
C4—C5—C6—N20.4 (3)C6—N2—Cu1—O297.30 (13)
O3—C7—C8—O41.3 (3)C2—N2—Cu1—O280.89 (10)
C5—C6—N2—C20.7 (2)C1—O1—Cu1—N25.29 (10)
C5—C6—N2—Cu1177.37 (12)C1—O1—Cu1—O284.83 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.86 (2)1.99 (2)2.8324 (16)168 (2)
N1—H1B···O4ii0.85 (2)2.53 (2)3.0678 (19)122 (2)
O2—H2A···O4iii0.81 (2)1.98 (2)2.7659 (17)165 (3)
O2—H2B···O3ii0.82 (2)2.05 (2)2.8264 (16)158 (2)
C6—H6···Cg1iv0.933.133.8251 (17)133
Symmetry codes: (i) x, y+1, z+1; (ii) x, y, z+1; (iii) x+1, y, z+1; (iv) x, y, z+1.
 

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