Di­aqua­bis­(pyridine-2-carbox­amide-κ2N1,O2)copper(II) squarate

Uçar, İ.; Bulut, A.; Yeşilel, O.Z.; Ölmez, H.I.; Büyükgüngör, O.

doi:10.1107/S1600536804030090

Diaquabis(pyridine-2-carboxamide-κ²N¹,O²)copper(II) squarate

İ. Uçar, A. Bulut, O. Z. Yeşilel, H. I. Ölmez and O. Büyükgüngör

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804030090/ci6487sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804030090/ci6487Isup2.hkl Contains datablock I

CCDC reference: 259075

checkCIF report

Key indicators

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

checkCIF/PLATON results

No syntax errors found



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
M_r = 455.87	F(000) = 233
Triclinic, P1	D_x = 1.784 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1240 (9) Å	Cell parameters from 13950 reflections
b = 7.7627 (9) Å	θ = 2.7–29.7°
c = 8.1191 (9) Å	µ = 1.35 mm⁻¹
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 tube	2241 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
Detector resolution: 6.67 pixels mm^-1	θ_max = 29.6°, θ_min = 2.7°
ω scans	h = −9→9
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→10
T_min = 0.656, T_max = 0.803	l = −11→11
8483 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0346P)² + 0.1621P] where P = (F_o² + 2F_c²)/3
2361 reflections	(Δ/σ)_max < 0.001
149 parameters	Δρ_max = 0.40 e Å⁻³
4 restraints	Δρ_min = −0.34 e Å⁻³

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	U_iso*/U_eq
C1	0.21475 (19)	0.32463 (17)	1.14790 (17)	0.0270 (2)
C2	0.16763 (18)	0.32436 (16)	0.96700 (17)	0.0244 (2)
C3	0.2272 (2)	0.45950 (18)	0.89902 (19)	0.0313 (3)
H3	0.3045	0.5614	0.9660	0.038*
C4	0.1698 (2)	0.4407 (2)	0.7288 (2)	0.0369 (3)
H4	0.2088	0.5298	0.6796	0.044*
C5	0.0547 (3)	0.2889 (2)	0.6333 (2)	0.0379 (3)
H5	0.0144	0.2740	0.5189	0.045*
C6	−0.0003 (2)	0.1586 (2)	0.71037 (19)	0.0330 (3)
H6	−0.0788	0.0562	0.6463	0.040*
C7	0.47741 (19)	−0.08788 (17)	0.37386 (17)	0.0262 (2)
C8	0.5383 (2)	0.10690 (17)	0.45315 (17)	0.0276 (3)
N1	0.3271 (2)	0.45972 (18)	1.25195 (18)	0.0374 (3)
N2	0.05588 (17)	0.17558 (15)	0.87345 (15)	0.0264 (2)
O1	0.14535 (16)	0.19543 (14)	1.19395 (13)	0.0343 (2)
O2	0.29209 (19)	−0.11154 (19)	0.93404 (17)	0.0439 (3)
O3	0.44753 (17)	−0.19531 (14)	0.22224 (13)	0.0354 (2)
O4	0.58527 (19)	0.23626 (15)	0.39787 (15)	0.0420 (3)
Cu1	0.0000	0.0000	1.0000	0.02944 (9)
H1A	0.366 (3)	0.556 (2)	1.228 (3)	0.046 (6)*
H1B	0.356 (4)	0.454 (4)	1.353 (2)	0.064 (7)*
H2A	0.345 (4)	−0.132 (4)	0.845 (3)	0.059 (7)*
H2B	0.359 (3)	−0.118 (3)	1.016 (2)	0.045 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0309 (6)	0.0227 (5)	0.0258 (6)	−0.0030 (5)	0.0004 (5)	0.0068 (5)
C2	0.0275 (6)	0.0196 (5)	0.0258 (6)	−0.0009 (4)	0.0030 (4)	0.0074 (4)
C3	0.0371 (7)	0.0229 (6)	0.0343 (7)	−0.0047 (5)	0.0028 (5)	0.0113 (5)
C4	0.0496 (8)	0.0296 (7)	0.0359 (7)	−0.0019 (6)	0.0052 (6)	0.0179 (6)
C5	0.0525 (9)	0.0352 (7)	0.0282 (7)	−0.0004 (6)	0.0007 (6)	0.0146 (6)
C6	0.0423 (7)	0.0285 (6)	0.0257 (6)	−0.0052 (5)	−0.0014 (5)	0.0077 (5)
C7	0.0318 (6)	0.0226 (5)	0.0235 (6)	−0.0032 (4)	−0.0015 (5)	0.0080 (5)
C8	0.0353 (6)	0.0235 (6)	0.0235 (6)	−0.0046 (5)	−0.0020 (5)	0.0091 (5)
N1	0.0467 (7)	0.0308 (6)	0.0312 (6)	−0.0141 (5)	−0.0086 (5)	0.0104 (5)
N2	0.0328 (5)	0.0213 (5)	0.0243 (5)	−0.0042 (4)	0.0018 (4)	0.0078 (4)
O1	0.0465 (6)	0.0289 (5)	0.0263 (5)	−0.0127 (4)	−0.0031 (4)	0.0113 (4)
O2	0.0471 (7)	0.0563 (7)	0.0341 (6)	0.0098 (6)	0.0054 (5)	0.0211 (6)
O3	0.0519 (6)	0.0274 (5)	0.0225 (5)	−0.0062 (4)	−0.0023 (4)	0.0046 (4)
O4	0.0668 (8)	0.0289 (5)	0.0309 (5)	−0.0125 (5)	−0.0020 (5)	0.0151 (4)
Cu1	0.04224 (15)	0.02166 (12)	0.02307 (12)	−0.01158 (9)	−0.00145 (9)	0.00909 (8)

Geometric parameters (Å, º) top

C1—O1	1.2489 (16)	C6—H6	0.93
C1—N1	1.3104 (18)	C7—O3	1.2523 (16)
C1—C2	1.4932 (19)	C7—C8	1.4687 (17)
C2—N2	1.3438 (16)	C8—O4	1.2495 (16)
C2—C3	1.3762 (18)	N1—H1A	0.855 (16)
C3—C4	1.385 (2)	N1—H1B	0.851 (17)
C3—H3	0.93	N2—Cu1	1.9724 (11)
C4—C5	1.375 (2)	O1—Cu1	1.9976 (10)
C4—H4	0.93	O2—Cu1	2.3342 (14)
C5—C6	1.385 (2)	O2—H2A	0.807 (17)
C5—H5	0.93	O2—H2B	0.816 (16)
C6—N2	1.3314 (18)

O1—C1—N1	122.56 (13)	C5—C6—H6	119.0
O1—C1—C2	118.50 (11)	O3—C7—C8	135.81 (13)
N1—C1—C2	118.94 (12)	O4—C8—C7	135.52 (13)
N2—C2—C3	122.03 (12)	C1—N1—H1A	124.5 (15)
N2—C2—C1	112.57 (11)	C1—N1—H1B	117.3 (18)
C3—C2—C1	125.40 (12)	H1A—N1—H1B	118 (2)
C2—C3—C4	118.68 (13)	C6—N2—C2	119.16 (12)
C2—C3—H3	120.7	C6—N2—Cu1	127.34 (9)
C4—C3—H3	120.7	C2—N2—Cu1	113.48 (9)
C5—C4—C3	119.31 (13)	C1—O1—Cu1	112.95 (9)
C5—C4—H4	120.3	Cu1—O2—H2A	129.6 (19)
C3—C4—H4	120.3	Cu1—O2—H2B	116.4 (16)
C4—C5—C6	118.86 (14)	H2A—O2—H2B	113 (3)
C4—C5—H5	120.6	N2—Cu1—O1	82.17 (4)
C6—C5—H5	120.6	N2—Cu1—O2	89.46 (5)
N2—C6—C5	121.96 (13)	O1—Cu1—O2	85.19 (5)
N2—C6—H6	119.0

O1—C1—C2—N2	−1.74 (19)	C3—C2—N2—C6	−0.5 (2)
N1—C1—C2—N2	178.17 (13)	C1—C2—N2—C6	178.82 (12)
O1—C1—C2—C3	177.57 (13)	C3—C2—N2—Cu1	177.84 (11)
N1—C1—C2—C3	−2.5 (2)	C1—C2—N2—Cu1	−2.83 (14)
N2—C2—C3—C4	0.0 (2)	N1—C1—O1—Cu1	−174.61 (12)
C1—C2—C3—C4	−179.29 (14)	C2—C1—O1—Cu1	5.30 (16)
C2—C3—C4—C5	0.4 (2)	C6—N2—Cu1—O1	−177.49 (14)
C3—C4—C5—C6	−0.2 (3)	C2—N2—Cu1—O1	4.32 (10)
C4—C5—C6—N2	−0.4 (3)	C6—N2—Cu1—O2	97.30 (13)
O3—C7—C8—O4	−1.3 (3)	C2—N2—Cu1—O2	−80.89 (10)
C5—C6—N2—C2	0.7 (2)	C1—O1—Cu1—N2	−5.29 (10)
C5—C6—N2—Cu1	−177.37 (12)	C1—O1—Cu1—O2	84.83 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.86 (2)	1.99 (2)	2.8324 (16)	168 (2)
N1—H1B···O4ⁱⁱ	0.85 (2)	2.53 (2)	3.0678 (19)	122 (2)
O2—H2A···O4ⁱⁱⁱ	0.81 (2)	1.98 (2)	2.7659 (17)	165 (3)
O2—H2B···O3ⁱⁱ	0.82 (2)	2.05 (2)	2.8264 (16)	158 (2)
C6—H6···Cg1^iv	0.93	3.13	3.8251 (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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Di­aqua­bis­(pyridine-2-carbox­amide-κ2N1,O2)copper(II) squarate

Supporting information

Key indicators

checkCIF/PLATON results

Diaquabis(pyridine-2-carboxamide-κ²N¹,O²)copper(II) squarate