Bis(N-oxido­nicotinamidium-κ²O,O′)diperchloratocopper(II)

The title compound, [Cu(ClO₄)₂(C₆H₆N₂O₂)₂], contains neutral mol­ecules of a centrosymmetric mononuclear copper(II) complex, in which the zwitterionic hydroxamic acid ligand is O,O′-chelated to the Cu^II atom. The Cu^II atom lies on an inversion centre and has a distorted tetragonal-bipyramidal environment, being coordinated by four O atoms of the two N-hydroxy­nicotinamide mol­ecules forming the equatorial plane, and by two O atoms of the perchlorate anions occupying the axial positions.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.032
• wR factor = 0.091
• Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cl1
PLAT301_ALERT_3_C Main Residue  Disorder .........................      16.00 Perc.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C5      ..       3.00 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  C6     ..  O4      ..       2.92 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 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
   4 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2003b); software used to prepare material for publication: SHELXL97.

Bis(N-hydroxynicotinamidium-κ²O,O')diperchloratocopper(II)

Crystal data

[Cu(ClO4)2(C6H6N2O2)2]	F(000) = 1084
Mr = 538.70	Dx = 1.985 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6668 reflections
a = 14.1287 (7) Å	θ = 1.0–27.5°
b = 8.6553 (3) Å	µ = 1.59 mm^−1
c = 15.7370 (8) Å	T = 120 K
β = 110.535 (2)°	Block, green
V = 1802.17 (14) Å^3	0.23 × 0.15 × 0.12 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	2057 independent reflections
Radiation source: fine-focus sealed tube	1746 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.037
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
φ scans, and ω scans with κ offset	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 2003a)	k = −11→11
Tmin = 0.710, Tmax = 0.832	l = −20→19
10729 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 2.0829P] where P = (Fo^2 + 2Fc^2)/3
2057 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.46 e Å^−3
3 restraints	Δρmin = −0.63 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	Occ. (<1)
Cu1	0.2500	0.7500	0.5000	0.01757 (14)
Cl1	−0.03389 (4)	0.76488 (5)	0.40513 (4)	0.02137 (16)
O1	0.27029 (11)	0.88460 (16)	0.60226 (9)	0.0197 (3)
O2	0.29805 (11)	0.92226 (15)	0.44917 (9)	0.0190 (3)
O3	0.05127 (13)	0.8602 (2)	0.41080 (13)	0.0376 (4)
O4	−0.0112 (15)	0.6128 (14)	0.3842 (13)	0.038 (3)	0.48 (4)
O5	−0.1253 (9)	0.819 (2)	0.3407 (12)	0.043 (3)	0.48 (4)
O6	−0.0343 (14)	0.7627 (19)	0.4973 (6)	0.037 (3)	0.48 (4)
O4B	−0.0174 (14)	0.6030 (11)	0.4091 (13)	0.039 (3)	0.52 (4)
O5B	−0.1136 (11)	0.799 (2)	0.3198 (8)	0.041 (2)	0.52 (4)
O6B	−0.0794 (17)	0.8070 (14)	0.4730 (12)	0.047 (4)	0.52 (4)
N1	0.32457 (13)	1.03670 (19)	0.51363 (11)	0.0167 (3)
H1N	0.360 (2)	1.110 (3)	0.5040 (17)	0.027 (6)*
N2	0.36369 (13)	1.1779 (2)	0.81671 (11)	0.0178 (3)
H2N	0.3600 (19)	1.147 (3)	0.8662 (18)	0.029 (7)*
C1	0.30986 (14)	1.0108 (2)	0.59012 (13)	0.0162 (4)
C2	0.33853 (14)	1.1282 (2)	0.66305 (13)	0.0160 (4)
C3	0.35754 (16)	1.2836 (2)	0.65181 (14)	0.0185 (4)
H3	0.3556	1.3205	0.5944	0.022*
C4	0.37929 (15)	1.3842 (2)	0.72515 (15)	0.0203 (4)
H4	0.3922	1.4903	0.7182	0.024*
C5	0.38190 (15)	1.3281 (2)	0.80821 (14)	0.0196 (4)
H5	0.3965	1.3955	0.8589	0.024*
C6	0.34182 (14)	1.0780 (2)	0.74764 (13)	0.0178 (4)
H6	0.3286	0.9728	0.7566	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0231 (2)	0.0171 (2)	0.0166 (2)	−0.00409 (12)	0.01207 (16)	−0.00280 (12)
Cl1	0.0266 (3)	0.0175 (3)	0.0242 (3)	−0.00120 (17)	0.0143 (2)	0.00224 (17)
O1	0.0255 (7)	0.0182 (7)	0.0192 (7)	−0.0051 (6)	0.0128 (6)	−0.0028 (5)
O2	0.0247 (7)	0.0182 (7)	0.0172 (7)	−0.0050 (6)	0.0110 (6)	−0.0046 (5)
O3	0.0312 (9)	0.0339 (9)	0.0533 (11)	−0.0089 (7)	0.0218 (8)	−0.0009 (8)
O4	0.030 (4)	0.024 (3)	0.046 (7)	0.004 (3)	−0.003 (4)	−0.010 (3)
O5	0.016 (2)	0.039 (5)	0.072 (6)	0.014 (2)	0.013 (4)	0.024 (5)
O6	0.045 (6)	0.050 (5)	0.022 (3)	−0.024 (4)	0.019 (3)	−0.007 (2)
O4B	0.031 (3)	0.019 (2)	0.058 (7)	0.0050 (17)	0.002 (5)	0.011 (3)
O5B	0.036 (4)	0.032 (4)	0.055 (4)	0.007 (3)	0.013 (3)	0.014 (3)
O6B	0.066 (8)	0.047 (4)	0.045 (5)	−0.020 (4)	0.042 (6)	−0.016 (3)
N1	0.0184 (8)	0.0168 (8)	0.0176 (8)	−0.0024 (6)	0.0098 (7)	−0.0024 (6)
N2	0.0211 (9)	0.0193 (8)	0.0154 (8)	−0.0011 (7)	0.0094 (7)	−0.0001 (7)
C1	0.0157 (9)	0.0164 (9)	0.0176 (9)	0.0021 (7)	0.0073 (7)	0.0008 (7)
C2	0.0152 (9)	0.0179 (9)	0.0163 (10)	0.0016 (7)	0.0072 (7)	−0.0002 (7)
C3	0.0188 (10)	0.0202 (9)	0.0193 (10)	0.0010 (8)	0.0102 (8)	0.0016 (8)
C4	0.0211 (10)	0.0171 (9)	0.0261 (10)	−0.0006 (8)	0.0126 (8)	−0.0007 (8)
C5	0.0196 (10)	0.0185 (10)	0.0222 (10)	−0.0009 (8)	0.0093 (8)	−0.0037 (8)
C6	0.0182 (10)	0.0167 (9)	0.0208 (10)	−0.0010 (7)	0.0098 (8)	−0.0008 (7)

Geometric parameters (Å, º)

Cu1—O1	1.9250 (13)	N1—C1	1.311 (3)
Cu1—O1^i	1.9250 (13)	N1—H1N	0.86 (3)
Cu1—O2	1.9248 (14)	N2—C6	1.337 (3)
Cu1—O2^i	1.9248 (14)	N2—C5	1.341 (3)
Cu1—O3	2.8282 (18)	N2—H2N	0.84 (3)
Cl1—O5	1.412 (10)	C1—C2	1.479 (3)
Cl1—O4B	1.418 (9)	C2—C6	1.385 (3)
Cl1—O4	1.420 (10)	C2—C3	1.395 (3)
Cl1—O3	1.4356 (16)	C3—C4	1.391 (3)
Cl1—O5B	1.449 (10)	C3—H3	0.9500
Cl1—O6	1.453 (5)	C4—C5	1.383 (3)
Cl1—O6B	1.473 (6)	C4—H4	0.9500
O1—C1	1.272 (2)	C5—H5	0.9500
O2—N1	1.373 (2)	C6—H6	0.9500
O2—Cu1—O2^i	180.00 (5)	C1—N1—H1N	125.5 (17)
O2—Cu1—O1	84.71 (6)	O2—N1—H1N	115.6 (17)
O2^i—Cu1—O1	95.29 (6)	C6—N2—C5	122.90 (18)
O2—Cu1—O1^i	95.29 (6)	C6—N2—H2N	118.2 (18)
O2^i—Cu1—O1^i	84.71 (6)	C5—N2—H2N	118.6 (18)
O1—Cu1—O1^i	180.0	O1—C1—N1	120.31 (17)
O2—Cu1—O3	88.05 (5)	O1—C1—C2	119.25 (17)
O2^i—Cu1—O3	91.95 (5)	N1—C1—C2	120.43 (17)
O1—Cu1—O3	92.39 (6)	C6—C2—C3	118.76 (18)
O1^i—Cu1—O3	87.61 (6)	C6—C2—C1	115.97 (17)
O5—Cl1—O4	111.2 (11)	C3—C2—C1	125.21 (18)
O5—Cl1—O3	113.0 (8)	C4—C3—C2	119.64 (19)
O4—Cl1—O3	107.1 (9)	C4—C3—H3	120.2
O4B—Cl1—O5B	107.8 (10)	C2—C3—H3	120.2
O5—Cl1—O6	113.5 (5)	C5—C4—C3	119.30 (19)
O4—Cl1—O6	107.5 (5)	C5—C4—H4	120.3
O3—Cl1—O6	104.0 (3)	C3—C4—H4	120.3
O4B—Cl1—O6B	108.6 (5)	N2—C5—C4	119.48 (18)
O5B—Cl1—O6B	103.1 (6)	N2—C5—H5	120.3
C1—O1—Cu1	109.79 (12)	C4—C5—H5	120.3
N1—O2—Cu1	107.25 (10)	N2—C6—C2	119.91 (18)
Cl1—O3—Cu1	120.10 (10)	N2—C6—H6	120.0
C1—N1—O2	117.72 (16)	C2—C6—H6	120.0
O2—Cu1—O1—C1	−4.25 (13)	Cu1—O1—C1—N1	4.3 (2)
O2^i—Cu1—O1—C1	175.75 (13)	Cu1—O1—C1—C2	−176.03 (13)
O3—Cu1—O1—C1	−92.07 (13)	O2—N1—C1—O1	−1.5 (3)
O1—Cu1—O2—N1	3.42 (11)	O2—N1—C1—C2	178.89 (16)
O1^i—Cu1—O2—N1	−176.58 (11)	O1—C1—C2—C6	14.5 (3)
O3—Cu1—O2—N1	95.99 (11)	N1—C1—C2—C6	−165.83 (17)
O5—Cl1—O3—Cu1	−165.3 (10)	O1—C1—C2—C3	−162.50 (19)
O4B—Cl1—O3—Cu1	−26.0 (9)	N1—C1—C2—C3	17.1 (3)
O4—Cl1—O3—Cu1	−42.4 (8)	C6—C2—C3—C4	0.0 (3)
O5B—Cl1—O3—Cu1	−147.0 (7)	C1—C2—C3—C4	176.98 (19)
O6—Cl1—O3—Cu1	71.2 (10)	C2—C3—C4—C5	0.1 (3)
O6B—Cl1—O3—Cu1	100.2 (11)	C6—N2—C5—C4	−0.7 (3)
O2—Cu1—O3—Cl1	168.24 (12)	C3—C4—C5—N2	0.2 (3)
O2^i—Cu1—O3—Cl1	−11.76 (12)	C5—N2—C6—C2	0.8 (3)
O1—Cu1—O3—Cl1	−107.14 (11)	C3—C2—C6—N2	−0.5 (3)
O1^i—Cu1—O3—Cl1	72.86 (11)	C1—C2—C6—N2	−177.73 (17)
Cu1—O2—N1—C1	−2.21 (19)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O6^ii	0.86 (3)	2.02 (3)	2.868 (6)	169 (3)
N1—H1N···O6B^ii	0.86 (3)	2.04 (3)	2.886 (7)	170 (3)
N2—H2N···O2^iii	0.84 (3)	1.90 (3)	2.704 (2)	158 (2)

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