Copper(II) bromide, nitrate and perchlorate com­plexes with sterically demanding N-(6-methyl­pyridin-2-yl)acetamide ligands

Functionalized acid amides are widely used in biology, medicine, environmental chemistry and many other areas. Among them, pyridine-substituted amides, in particular N-(pyridin-2-yl)acetamide and its derivatives, play an important role due to their excellent chelating properties. The donor properties of these ligands can be effectively modified by introducing electron-donating substituents (e.g. alkyl groups) into the heterocycle. On the other hand, substituents in the α-position of the pyridine ring can create steric hindrance, which significantly influences the coordination number and geometry. To achieve a better under­standing of these effects, copper(II) complexes with sterically demanding N-(6-methyl­pyridin-2-yl)acetamide ligands (L) and monoanions of different size, shape and coordination ability have been chosen as model compounds. The crystal structures of three new compounds, bromido­bis­[N-(6-methyl­pyridin-2-yl-κN)acetamide-κO]copper(II) bromide, [CuBr(C₈H₁₀N₂O)]Br, (I), aqua­bis­[N-(6-methyl­pyridin-2-yl-κN)acetamide-κO]copper(II) dinitrate, [Cu(C₈H₁₀N₂O)(H₂O)](NO₃)₂, (II), and aqua­bis­[N-(6-methyl­pyridin-2-yl-κN)acetamide-κO]copper(II) bis­(perchlorate), [Cu(C₈H₁₀N₂O)(H₂O)](ClO₄)₂, (III), have been determined by single-crystal X-ray diffraction analysis. It has been shown that the presence of the 6-methyl group results in either a distorted square-pyramidal or a distorted trigonal–bipyramidal coordination geometry around the Cu^II centres instead of the typical octa­hedral geometry observed when the methyl substituent is absent or occupies any other position on the pyridine ring. Moreover, due to the steric hindrance provided by the L ligands, only the bromide ligand, the smallest of the series, enters into the first coordination sphere of the Cu^II ion in (I). In (II) and (III), the vacant coordination site of the Cu^II ion is occupied by a water mol­ecule, while the nitrate and perchlorate anions are not involved in coordination to the metal centre. The structures of (I)–(III) are characterized by the presence of one-dimensional infinite chains formed by hydrogen bonds of the types N—H...Br [in (I)], N—H...O and O—H...O [in (II) and (III)] between the amide groups of the L ligands, the coordinated water mol­ecules and the uncoordinated anions. The hydrogen-bonded chains are further inter­connected through π–π stacking inter­actions between the pyridine rings of the L ligands, with approximate inter­planar separations of 3.5–3.6 Å.

Computing details

For all structures, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Bruker, 2004; Sheldrick, 2015); program(s) used to refine structure: SHELXTL (Bruker, 2004; Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Bruker, 2004; Sheldrick, 2015).

Bromidobis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bromide (1)

Crystal data

[CuBr(C8H10N2O)2]Br	Z = 2
Mr = 523.72	F(000) = 518
Triclinic, P1	Dx = 1.775 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0673 (12) Å	Cell parameters from 5072 reflections
b = 10.1144 (14) Å	θ = 2.3–27.6°
c = 11.7417 (14) Å	µ = 5.21 mm^−1
α = 69.013 (5)°	T = 296 K
β = 77.791 (5)°	Plate, brown
γ = 81.901 (5)°	0.35 × 0.20 × 0.02 mm
V = 980.2 (2) Å^3

Data collection

Bruker Nonius X8 APEX CCD area-detector diffractometer	4436 independent reflections
Radiation source: fine-focus sealed tube	3569 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 25 pixels mm^-1	θmax = 27.7°, θmin = 2.3°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→13
Tmin = 0.263, Tmax = 0.903	l = −12→15
10439 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.042P)^2 + 0.4667P] where P = (Fo^2 + 2Fc^2)/3
4436 reflections	(Δ/σ)max < 0.001
230 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.96 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1	0.43216 (4)	0.30182 (4)	0.01955 (3)	0.05539 (12)
Br2	−0.26809 (4)	0.58501 (4)	0.35313 (4)	0.05613 (12)
Cu1	0.27507 (4)	0.16494 (3)	0.20270 (3)	0.03078 (10)
O1	0.1365 (2)	0.1547 (2)	0.36932 (19)	0.0443 (5)
O2	0.2495 (2)	−0.0530 (2)	0.2521 (2)	0.0467 (6)
N1	0.0848 (3)	0.2317 (2)	0.1274 (2)	0.0323 (5)
N2	−0.0147 (3)	0.3446 (2)	0.2768 (2)	0.0369 (6)
H2	−0.0546	0.4250	0.2819	0.044*
N3	0.4527 (3)	0.1134 (2)	0.2929 (2)	0.0308 (5)
N4	0.4876 (3)	−0.1248 (2)	0.2904 (2)	0.0394 (6)
H4	0.5567	−0.1918	0.2879	0.047*
C1	−0.0203 (3)	0.3210 (3)	0.1677 (3)	0.0327 (6)
C2	−0.1395 (3)	0.3904 (3)	0.1073 (3)	0.0413 (7)
H2A	−0.2086	0.4527	0.1370	0.050*
C3	−0.1536 (4)	0.3658 (4)	0.0033 (3)	0.0505 (8)
H3	−0.2319	0.4121	−0.0395	0.061*
C4	−0.0507 (4)	0.2718 (4)	−0.0373 (3)	0.0514 (9)
H4A	−0.0606	0.2528	−0.1071	0.062*
C5	0.0678 (4)	0.2050 (3)	0.0251 (3)	0.0408 (7)
C6	0.1786 (5)	0.1010 (4)	−0.0187 (4)	0.0579 (9)
H6A	0.2796	0.1276	−0.0301	0.087*
H6B	0.1589	0.1011	−0.0959	0.087*
H6C	0.1681	0.0076	0.0419	0.087*
C7	0.0460 (3)	0.2562 (3)	0.3755 (3)	0.0361 (6)
C8	−0.0019 (4)	0.2854 (4)	0.4944 (3)	0.0546 (9)
H8A	−0.0327	0.1997	0.5600	0.082*
H8B	−0.0850	0.3564	0.4870	0.082*
H8C	0.0813	0.3188	0.5127	0.082*
C9	0.5347 (3)	−0.0119 (3)	0.3137 (3)	0.0337 (6)
C10	0.6668 (4)	−0.0379 (3)	0.3617 (3)	0.0492 (8)
H10	0.7223	−0.1249	0.3729	0.059*
C11	0.7157 (4)	0.0647 (4)	0.3925 (4)	0.0559 (10)
H11	0.8044	0.0486	0.4248	0.067*
C12	0.6308 (4)	0.1925 (3)	0.3746 (3)	0.0450 (8)
H12	0.6606	0.2629	0.3967	0.054*
C13	0.5020 (3)	0.2154 (3)	0.3241 (3)	0.0363 (6)
C14	0.4137 (4)	0.3562 (3)	0.3021 (4)	0.0541 (9)
H14A	0.3770	0.3713	0.3797	0.081*
H14B	0.3296	0.3576	0.2637	0.081*
H14C	0.4778	0.4301	0.2487	0.081*
C15	0.3528 (3)	−0.1463 (3)	0.2714 (3)	0.0345 (6)
C16	0.3361 (4)	−0.2932 (3)	0.2760 (3)	0.0480 (8)
H16A	0.2361	−0.2991	0.2640	0.072*
H16B	0.3523	−0.3599	0.3552	0.072*
H16C	0.4092	−0.3148	0.2118	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0420 (2)	0.0658 (2)	0.0432 (2)	−0.01122 (17)	−0.00237 (15)	−0.00054 (16)
Br2	0.0585 (2)	0.0443 (2)	0.0718 (3)	0.02596 (16)	−0.02546 (19)	−0.03025 (17)
Cu1	0.02643 (18)	0.02570 (17)	0.0359 (2)	0.00479 (13)	−0.00552 (14)	−0.00774 (14)
O1	0.0406 (12)	0.0437 (12)	0.0349 (11)	0.0194 (10)	−0.0054 (9)	−0.0058 (9)
O2	0.0357 (12)	0.0266 (10)	0.0743 (16)	0.0041 (9)	−0.0132 (11)	−0.0132 (10)
N1	0.0286 (12)	0.0283 (11)	0.0372 (13)	0.0003 (9)	−0.0066 (10)	−0.0081 (10)
N2	0.0349 (13)	0.0308 (12)	0.0423 (14)	0.0120 (10)	−0.0095 (11)	−0.0128 (10)
N3	0.0298 (12)	0.0262 (11)	0.0342 (12)	0.0029 (9)	−0.0050 (10)	−0.0099 (9)
N4	0.0373 (14)	0.0284 (12)	0.0534 (16)	0.0114 (10)	−0.0114 (12)	−0.0180 (11)
C1	0.0275 (14)	0.0288 (13)	0.0366 (15)	0.0018 (11)	−0.0062 (12)	−0.0059 (11)
C2	0.0298 (15)	0.0371 (16)	0.0478 (18)	0.0038 (12)	−0.0088 (13)	−0.0045 (13)
C3	0.0415 (19)	0.053 (2)	0.054 (2)	−0.0002 (15)	−0.0228 (16)	−0.0078 (16)
C4	0.054 (2)	0.055 (2)	0.051 (2)	−0.0086 (17)	−0.0197 (17)	−0.0179 (16)
C5	0.0414 (17)	0.0386 (16)	0.0452 (18)	−0.0062 (13)	−0.0103 (14)	−0.0147 (13)
C6	0.067 (3)	0.056 (2)	0.062 (2)	0.0047 (18)	−0.0163 (19)	−0.0346 (19)
C7	0.0256 (14)	0.0399 (16)	0.0381 (16)	0.0051 (12)	−0.0040 (12)	−0.0111 (12)
C8	0.050 (2)	0.065 (2)	0.047 (2)	0.0217 (17)	−0.0119 (16)	−0.0246 (17)
C9	0.0321 (15)	0.0261 (13)	0.0376 (16)	0.0048 (11)	−0.0069 (12)	−0.0066 (11)
C10	0.0411 (18)	0.0331 (16)	0.068 (2)	0.0074 (13)	−0.0241 (17)	−0.0059 (15)
C11	0.049 (2)	0.0467 (19)	0.067 (2)	−0.0063 (16)	−0.0292 (18)	−0.0024 (17)
C12	0.051 (2)	0.0395 (17)	0.0436 (18)	−0.0115 (15)	−0.0144 (15)	−0.0071 (13)
C13	0.0407 (17)	0.0294 (14)	0.0347 (15)	−0.0025 (12)	−0.0023 (13)	−0.0082 (12)
C14	0.053 (2)	0.0351 (17)	0.082 (3)	0.0027 (15)	−0.0124 (19)	−0.0314 (17)
C15	0.0380 (16)	0.0261 (13)	0.0352 (15)	0.0017 (12)	−0.0012 (12)	−0.0099 (11)
C16	0.053 (2)	0.0316 (16)	0.062 (2)	0.0019 (14)	−0.0075 (17)	−0.0223 (15)

Geometric parameters (Å, º)

Cu1—O1	2.066 (2)	C5—C6	1.501 (5)
Cu1—O2	2.102 (2)	C6—H6A	0.9600
Cu1—N1	2.026 (2)	C6—H6B	0.9600
Cu1—N3	2.019 (2)	C6—H6C	0.9600
Cu1—Br1	2.3870 (5)	C7—C8	1.493 (4)
O1—C7	1.234 (3)	C8—H8A	0.9600
O2—C15	1.227 (3)	C8—H8B	0.9600
N1—C1	1.350 (4)	C8—H8C	0.9600
N1—C5	1.364 (4)	C9—C10	1.383 (4)
N2—C7	1.354 (4)	C10—C11	1.368 (5)
N2—C1	1.396 (4)	C10—H10	0.9300
N2—H2	0.8600	C11—C12	1.379 (5)
N3—C9	1.345 (3)	C11—H11	0.9300
N3—C13	1.367 (4)	C12—C13	1.374 (4)
N4—C15	1.348 (4)	C12—H12	0.9300
N4—C9	1.403 (4)	C13—C14	1.497 (4)
N4—H4	0.8600	C14—H14A	0.9600
C1—C2	1.385 (4)	C14—H14B	0.9600
C2—C3	1.364 (5)	C14—H14C	0.9600
C2—H2A	0.9300	C15—C16	1.495 (4)
C3—C4	1.375 (5)	C16—H16A	0.9600
C3—H3	0.9300	C16—H16B	0.9600
C4—C5	1.387 (5)	C16—H16C	0.9600
C4—H4A	0.9300
O1—Cu1—O2	86.95 (9)	C5—C6—H6C	109.5
O1—Cu1—N1	85.88 (9)	H6A—C6—H6C	109.5
O1—Cu1—N3	87.94 (9)	H6B—C6—H6C	109.5
O2—Cu1—N1	95.63 (9)	O1—C7—N2	122.3 (3)
O2—Cu1—N3	88.53 (9)	O1—C7—C8	120.5 (3)
N1—Cu1—N3	172.35 (9)	N2—C7—C8	117.2 (3)
O1—Cu1—Br1	148.28 (7)	C7—C8—H8A	109.5
O2—Cu1—Br1	124.62 (7)	C7—C8—H8B	109.5
N1—Cu1—Br1	93.11 (7)	H8A—C8—H8B	109.5
N3—Cu1—Br1	89.78 (7)	C7—C8—H8C	109.5
C7—O1—Cu1	119.47 (19)	H8A—C8—H8C	109.5
C15—O2—Cu1	124.57 (19)	H8B—C8—H8C	109.5
C1—N1—C5	117.8 (3)	N3—C9—C10	122.2 (3)
C1—N1—Cu1	119.79 (19)	N3—C9—N4	121.2 (3)
C5—N1—Cu1	121.8 (2)	C10—C9—N4	116.5 (3)
C7—N2—C1	127.9 (2)	C11—C10—C9	119.8 (3)
C7—N2—H2	116.0	C11—C10—H10	120.1
C1—N2—H2	116.0	C9—C10—H10	120.1
C9—N3—C13	117.7 (2)	C10—C11—C12	118.6 (3)
C9—N3—Cu1	123.50 (19)	C10—C11—H11	120.7
C13—N3—Cu1	118.54 (19)	C12—C11—H11	120.7
C15—N4—C9	131.2 (2)	C13—C12—C11	119.8 (3)
C15—N4—H4	114.4	C13—C12—H12	120.1
C9—N4—H4	114.4	C11—C12—H12	120.1
N1—C1—C2	123.1 (3)	N3—C13—C12	121.8 (3)
N1—C1—N2	120.3 (2)	N3—C13—C14	119.1 (3)
C2—C1—N2	116.6 (3)	C12—C13—C14	119.0 (3)
C3—C2—C1	118.8 (3)	C13—C14—H14A	109.5
C3—C2—H2A	120.6	C13—C14—H14B	109.5
C1—C2—H2A	120.6	H14A—C14—H14B	109.5
C2—C3—C4	119.2 (3)	C13—C14—H14C	109.5
C2—C3—H3	120.4	H14A—C14—H14C	109.5
C4—C3—H3	120.4	H14B—C14—H14C	109.5
C3—C4—C5	120.4 (3)	O2—C15—N4	123.0 (3)
C3—C4—H4A	119.8	O2—C15—C16	121.6 (3)
C5—C4—H4A	119.8	N4—C15—C16	115.4 (3)
N1—C5—C4	120.7 (3)	C15—C16—H16A	109.5
N1—C5—C6	119.1 (3)	C15—C16—H16B	109.5
C4—C5—C6	120.1 (3)	H16A—C16—H16B	109.5
C5—C6—H6A	109.5	C15—C16—H16C	109.5
C5—C6—H6B	109.5	H16A—C16—H16C	109.5
H6A—C6—H6B	109.5	H16B—C16—H16C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br2	0.86	2.54	3.334 (2)	153
N4—H4···Br2^i	0.86	2.54	3.373 (2)	162

Symmetry code: (i) x+1, y−1, z.

Aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) dinitrate (2)

Crystal data

[Cu(C8H10N2O)(H2O)](NO3)2	F(000) = 1044
Mr = 505.94	Dx = 1.612 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 8020 reflections
a = 13.3089 (2) Å	θ = 2.7–27.4°
b = 8.4494 (1) Å	µ = 1.11 mm^−1
c = 18.5350 (3) Å	T = 296 K
V = 2084.30 (5) Å^3	Block, blue
Z = 4	0.30 × 0.20 × 0.15 mm

Data collection

Bruker Nonius X8 APEX CCD area-detector diffractometer	2388 independent reflections
Radiation source: fine-focus sealed tube	2055 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 25 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
φ and ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −10→6
Tmin = 0.732, Tmax = 0.851	l = −23→24
14975 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0591P)^2 + 1.478P] where P = (Fo^2 + 2Fc^2)/3
2388 reflections	(Δ/σ)max = 0.001
152 parameters	Δρmax = 0.69 e Å^−3
14 restraints	Δρmin = −0.60 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cu1	0.0000	0.48557 (4)	0.2500	0.02844 (14)
O1	−0.06427 (12)	0.3343 (2)	0.32072 (8)	0.0426 (4)
N1	0.12902 (13)	0.4770 (2)	0.31011 (9)	0.0296 (4)
C1	0.13291 (16)	0.4172 (2)	0.37760 (11)	0.0324 (4)
O2	0.05962 (16)	0.9038 (2)	0.13733 (9)	0.0544 (5)
N2	0.04725 (14)	0.3606 (2)	0.41237 (9)	0.0359 (4)
H2	0.0536	0.3468	0.4581	0.043*
C2	0.22143 (18)	0.4104 (3)	0.41722 (13)	0.0473 (6)
H2A	0.2212	0.3703	0.4640	0.057*
O3	0.0421 (2)	0.6855 (2)	0.07703 (11)	0.0677 (6)
N3	0.07487 (16)	0.8226 (3)	0.08211 (10)	0.0435 (5)
C3	0.3092 (2)	0.4632 (4)	0.38677 (16)	0.0544 (7)
H3	0.3694	0.4587	0.4123	0.065*
O4	0.1245 (2)	0.8752 (3)	0.03201 (13)	0.0934 (9)
C4	0.30655 (18)	0.5228 (3)	0.31794 (15)	0.0460 (6)
H4	0.3654	0.5582	0.2962	0.055*
C5	0.21673 (17)	0.5304 (3)	0.28094 (12)	0.0348 (5)
C6	0.21686 (19)	0.5998 (3)	0.20645 (13)	0.0482 (6)
H6A	0.1580	0.5653	0.1810	0.072*
H6B	0.2758	0.5653	0.1811	0.072*
H6C	0.2169	0.7132	0.2096	0.072*
C7	−0.04313 (17)	0.3246 (2)	0.38578 (11)	0.0330 (4)
C8	−0.1201 (2)	0.2691 (3)	0.43859 (12)	0.0469 (6)
H8A	−0.1839	0.3160	0.4272	0.070*
H8B	−0.1005	0.2998	0.4864	0.070*
H8C	−0.1256	0.1560	0.4361	0.070*
O1W	0.0000	0.7201 (3)	0.2500	0.0426 (6)
H1W	0.015 (3)	0.779 (3)	0.2186 (8)	0.076 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0264 (2)	0.0360 (2)	0.0229 (2)	0.000	−0.00321 (12)	0.000
O1	0.0444 (9)	0.0588 (10)	0.0247 (7)	−0.0160 (8)	−0.0059 (6)	0.0096 (7)
N1	0.0292 (8)	0.0358 (9)	0.0238 (8)	0.0005 (6)	−0.0016 (7)	−0.0004 (6)
C1	0.0335 (10)	0.0355 (10)	0.0282 (9)	0.0019 (8)	−0.0048 (8)	−0.0008 (8)
O2	0.0754 (13)	0.0533 (11)	0.0344 (9)	−0.0085 (9)	0.0091 (9)	−0.0042 (7)
N2	0.0393 (10)	0.0468 (10)	0.0216 (8)	−0.0009 (8)	−0.0052 (7)	0.0071 (7)
C2	0.0411 (13)	0.0649 (16)	0.0360 (12)	0.0025 (11)	−0.0131 (10)	0.0040 (11)
O3	0.0954 (17)	0.0526 (11)	0.0552 (12)	−0.0178 (12)	−0.0198 (12)	−0.0037 (9)
N3	0.0515 (12)	0.0494 (11)	0.0297 (9)	−0.0022 (9)	−0.0040 (8)	0.0011 (8)
C3	0.0348 (13)	0.0780 (19)	0.0502 (15)	0.0019 (12)	−0.0154 (11)	−0.0045 (14)
O4	0.144 (2)	0.0793 (16)	0.0571 (13)	−0.0192 (16)	0.0470 (16)	−0.0052 (12)
C4	0.0277 (11)	0.0615 (15)	0.0487 (14)	−0.0038 (10)	−0.0003 (10)	−0.0059 (11)
C5	0.0308 (10)	0.0410 (11)	0.0327 (11)	−0.0018 (8)	0.0007 (9)	−0.0035 (9)
C6	0.0375 (12)	0.0661 (16)	0.0409 (13)	−0.0073 (11)	0.0072 (10)	0.0108 (11)
C7	0.0378 (11)	0.0346 (10)	0.0267 (9)	−0.0007 (8)	0.0004 (8)	0.0046 (8)
C8	0.0508 (14)	0.0586 (14)	0.0314 (11)	−0.0096 (11)	0.0060 (10)	0.0073 (10)
O1W	0.0629 (16)	0.0357 (12)	0.0293 (12)	0.000	0.0088 (10)	0.000

Geometric parameters (Å, º)

Cu1—O1^i	2.0205 (15)	O3—N3	1.241 (3)
Cu1—O1	2.0206 (15)	N3—O4	1.223 (3)
Cu1—O1W	1.982 (3)	C3—C4	1.372 (4)
Cu1—N1	2.0482 (17)	C3—H3	0.9300
Cu1—N1^i	2.0482 (17)	C4—C5	1.380 (3)
O1—C7	1.241 (2)	C4—H4	0.9300
N1—C1	1.350 (3)	C5—C6	1.500 (3)
N1—C5	1.363 (3)	C6—H6A	0.9600
C1—C2	1.389 (3)	C6—H6B	0.9600
C1—N2	1.394 (3)	C6—H6C	0.9600
O2—N3	1.249 (3)	C7—C8	1.493 (3)
N2—C7	1.335 (3)	C8—H8A	0.9600
N2—H2	0.8600	C8—H8B	0.9600
C2—C3	1.372 (4)	C8—H8C	0.9600
C2—H2A	0.9300	O1W—H1W	0.790 (16)
O1—Cu1—O1^i	101.54 (11)	C4—C3—C2	118.7 (2)
O1—Cu1—O1W^i	129.23 (5)	C4—C3—H3	120.7
O1—Cu1—O1W	129.23 (5)	C2—C3—H3	120.7
O1—Cu1—N1	88.84 (7)	C3—C4—C5	120.1 (2)
O1—Cu1—N1^i	88.61 (6)	C3—C4—H4	119.9
N1—Cu1—O1W	92.02 (5)	C5—C4—H4	119.9
N1^i—Cu1—O1W	92.02 (5)	N1—C5—C4	122.0 (2)
O1^i—Cu1—N1^i	88.84 (7)	N1—C5—C6	119.69 (19)
O1—Cu1—N1^i	88.61 (6)	C4—C5—C6	118.3 (2)
N1—Cu1—N1^i	175.96 (10)	C5—C6—H6A	109.5
C7—O1—Cu1	125.19 (15)	C5—C6—H6B	109.5
C1—N1—C5	117.29 (18)	H6A—C6—H6B	109.5
C1—N1—Cu1	123.32 (14)	C5—C6—H6C	109.5
C5—N1—Cu1	119.37 (14)	H6A—C6—H6C	109.5
N1—C1—C2	122.5 (2)	H6B—C6—H6C	109.5
N1—C1—N2	121.69 (18)	O1—C7—N2	123.2 (2)
C2—C1—N2	115.78 (19)	O1—C7—C8	120.1 (2)
C7—N2—C1	130.12 (17)	N2—C7—C8	116.63 (19)
C7—N2—H2	114.9	C7—C8—H8A	109.5
C1—N2—H2	114.9	C7—C8—H8B	109.5
C3—C2—C1	119.4 (2)	H8A—C8—H8B	109.5
C3—C2—H2A	120.3	C7—C8—H8C	109.5
C1—C2—H2A	120.3	H8A—C8—H8C	109.5
O4—N3—O3	118.1 (2)	H8B—C8—H8C	109.5
O4—N3—O2	120.7 (2)	Cu1—O1W—H1W	129.0 (17)
O3—N3—O2	121.2 (2)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2	0.79 (2)	1.93 (2)	2.720 (2)	174 (3)
N2—H2···O3^ii	0.86	2.23	3.078 (3)	170

Symmetry code: (ii) x, −y+1, z+1/2.

Aquabis[N-(6-methylpyridin-2-yl-κN)acetamide-κO]copper(II) bis(perchlorate) (3)

Crystal data

[Cu(C8H10N2O)(H2O)](ClO4)2	F(000) = 1188
Mr = 580.82	Dx = 1.677 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6860 reflections
a = 18.7332 (4) Å	θ = 2.3–27.4°
b = 8.2315 (2) Å	µ = 1.25 mm^−1
c = 15.7876 (3) Å	T = 296 K
β = 109.100 (1)°	Plate, green
V = 2300.46 (9) Å^3	0.35 × 0.33 × 0.02 mm
Z = 4

Data collection

Bruker Nonius X8 APEX CCD area-detector diffractometer	2647 independent reflections
Radiation source: fine-focus sealed tube	2396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 25 pixels mm^-1	θmax = 27.5°, θmin = 2.3°
φ and ω scans	h = −24→24
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −10→10
Tmin = 0.669, Tmax = 0.976	l = −20→15
12928 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.078P)^2 + 3.0728P] where P = (Fo^2 + 2Fc^2)/3
2647 reflections	(Δ/σ)max < 0.001
182 parameters	Δρmax = 0.69 e Å^−3
43 restraints	Δρmin = −0.80 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.0000	0.40227 (6)	0.2500	0.03092 (17)
Cl1	0.16549 (4)	0.97240 (10)	0.38576 (6)	0.0505 (2)
O1	0.10379 (11)	0.4374 (3)	0.25674 (13)	0.0367 (4)
N1	0.03439 (12)	0.3477 (3)	0.38138 (13)	0.0300 (4)
C1	0.09602 (16)	0.4188 (3)	0.43816 (18)	0.0342 (6)
N2	0.14813 (13)	0.4959 (3)	0.40559 (16)	0.0382 (5)
H2	0.1799	0.5590	0.4428	0.046*
C2	0.1134 (2)	0.4130 (4)	0.5306 (2)	0.0509 (8)
H2A	0.1555	0.4670	0.5682	0.061*
C3	0.0673 (2)	0.3264 (5)	0.5652 (2)	0.0570 (9)
H3	0.0765	0.3242	0.6267	0.068*
O4	0.1903 (2)	1.1255 (4)	0.3679 (3)	0.0871 (11)
C4	0.0070 (2)	0.2423 (4)	0.5083 (2)	0.0510 (8)
H4	−0.0233	0.1787	0.5315	0.061*
C5	−0.00827 (16)	0.2527 (4)	0.41665 (19)	0.0389 (6)
C6	−0.0702 (2)	0.1537 (5)	0.3546 (3)	0.0599 (10)
H6A	−0.1156	0.2173	0.3345	0.090*
H6B	−0.0788	0.0591	0.3855	0.090*
H6C	−0.0561	0.1209	0.3039	0.090*
C7	0.15514 (15)	0.4845 (3)	0.32373 (19)	0.0361 (6)
C8	0.22995 (19)	0.5304 (5)	0.3165 (3)	0.0571 (9)
H8A	0.2581	0.4338	0.3145	0.086*
H8B	0.2574	0.5945	0.3676	0.086*
H8C	0.2225	0.5923	0.2628	0.086*
O1A	0.1225 (6)	0.9858 (14)	0.4420 (7)	0.091 (2)	0.382 (4)
O2A	0.1277 (7)	0.8814 (19)	0.3054 (7)	0.080 (2)	0.382 (4)
O3A	0.2352 (5)	0.8779 (13)	0.4281 (7)	0.065 (2)	0.382 (4)
O1B	0.0893 (4)	0.9825 (14)	0.3852 (7)	0.091 (2)	0.434 (5)
O2B	0.1535 (6)	0.8770 (15)	0.3029 (5)	0.080 (2)	0.434 (5)
O3B	0.2152 (4)	0.8806 (10)	0.4531 (5)	0.065 (2)	0.434 (5)
O1W	0.0000	0.6956 (4)	0.2500	0.0539 (8)
H1W	0.0335 (11)	0.756 (4)	0.278 (2)	0.067 (13)*
O3C	0.1899 (10)	0.9364 (17)	0.4787 (6)	0.065 (2)	0.183 (5)
O2C	0.2013 (9)	0.870 (2)	0.3418 (12)	0.080 (2)	0.183 (5)
O1C	0.0863 (5)	0.955 (3)	0.3509 (16)	0.091 (2)	0.183 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0231 (2)	0.0445 (3)	0.0228 (2)	0.000	0.00420 (17)	0.000
Cl1	0.0383 (4)	0.0443 (4)	0.0626 (5)	0.0008 (3)	0.0081 (3)	0.0122 (3)
O1	0.0270 (9)	0.0497 (11)	0.0334 (10)	−0.0012 (8)	0.0098 (8)	−0.0023 (8)
N1	0.0272 (10)	0.0345 (10)	0.0255 (10)	0.0021 (8)	0.0049 (8)	0.0022 (8)
C1	0.0330 (13)	0.0370 (13)	0.0286 (12)	0.0047 (10)	0.0049 (10)	−0.0017 (10)
N2	0.0314 (11)	0.0414 (12)	0.0354 (12)	−0.0071 (10)	0.0021 (9)	−0.0070 (10)
C2	0.0513 (19)	0.065 (2)	0.0281 (14)	0.0027 (15)	0.0019 (13)	−0.0079 (13)
C3	0.069 (2)	0.074 (2)	0.0288 (14)	0.0125 (19)	0.0180 (14)	0.0038 (15)
O4	0.080 (2)	0.0534 (15)	0.114 (3)	−0.0116 (15)	0.0142 (19)	0.0178 (16)
C4	0.0557 (19)	0.0606 (19)	0.0445 (16)	0.0104 (16)	0.0269 (15)	0.0158 (15)
C5	0.0357 (14)	0.0430 (14)	0.0380 (14)	0.0043 (11)	0.0122 (11)	0.0086 (11)
C6	0.0489 (19)	0.062 (2)	0.061 (2)	−0.0198 (17)	0.0078 (16)	0.0179 (18)
C7	0.0277 (13)	0.0354 (13)	0.0430 (14)	0.0011 (10)	0.0087 (11)	−0.0006 (11)
C8	0.0333 (16)	0.068 (2)	0.072 (2)	−0.0098 (15)	0.0187 (16)	−0.0068 (19)
O1A	0.070 (3)	0.113 (4)	0.103 (5)	0.004 (3)	0.044 (3)	0.015 (4)
O2A	0.071 (5)	0.084 (3)	0.074 (3)	−0.011 (4)	0.010 (3)	−0.004 (2)
O3A	0.064 (4)	0.052 (2)	0.058 (4)	0.009 (2)	−0.007 (3)	−0.003 (3)
O1B	0.070 (3)	0.113 (4)	0.103 (5)	0.004 (3)	0.044 (3)	0.015 (4)
O2B	0.071 (5)	0.084 (3)	0.074 (3)	−0.011 (4)	0.010 (3)	−0.004 (2)
O3B	0.064 (4)	0.052 (2)	0.058 (4)	0.009 (2)	−0.007 (3)	−0.003 (3)
O1W	0.0431 (18)	0.0414 (17)	0.069 (2)	0.000	0.0069 (16)	0.000
O3C	0.064 (4)	0.052 (2)	0.058 (4)	0.009 (2)	−0.007 (3)	−0.003 (3)
O2C	0.071 (5)	0.084 (3)	0.074 (3)	−0.011 (4)	0.010 (3)	−0.004 (2)
O1C	0.070 (3)	0.113 (4)	0.103 (5)	0.004 (3)	0.044 (3)	0.015 (4)

Geometric parameters (Å, º)

Cu1—O1^i	1.934 (2)	C1—N2	1.396 (4)
Cu1—O1	1.934 (2)	N2—C7	1.345 (4)
Cu1—O1W	2.414 (3)	N2—H2	0.8600
Cu1—N1	2.011 (2)	C2—C3	1.363 (5)
Cu1—N1^i	2.011 (2)	C2—H2A	0.9300
Cl1—O1A	1.386 (7)	C3—C4	1.377 (5)
Cl1—O3B	1.386 (6)	C3—H3	0.9300
Cl1—O2C	1.396 (10)	C4—C5	1.383 (4)
Cl1—O4	1.403 (3)	C4—H4	0.9300
Cl1—O1C	1.411 (10)	C5—C6	1.492 (5)
Cl1—O3C	1.418 (8)	C6—H6A	0.9600
Cl1—O1B	1.428 (6)	C6—H6B	0.9600
Cl1—O2A	1.444 (7)	C6—H6C	0.9600
Cl1—O2B	1.479 (5)	C7—C8	1.492 (4)
Cl1—O3A	1.479 (7)	C8—H8A	0.9600
O1—C7	1.236 (3)	C8—H8B	0.9600
N1—C1	1.342 (3)	C8—H8C	0.9600
N1—C5	1.360 (4)	O1W—H1W	0.81 (2)
C1—C2	1.389 (4)
O1—Cu1—O1^i	162.78 (13)	N1—C1—N2	120.3 (2)
O1^i—Cu1—O1W	81.39 (6)	C2—C1—N2	116.8 (3)
O1—Cu1—O1W	81.39 (6)	C7—N2—C1	128.5 (2)
O1^i—Cu1—N1	93.85 (8)	C7—N2—H2	115.8
O1—Cu1—N1	89.98 (8)	C1—N2—H2	115.8
O1^i—Cu1—N1^i	89.98 (8)	C3—C2—C1	118.5 (3)
O1—Cu1—N1^i	93.85 (8)	C3—C2—H2A	120.8
N1—Cu1—O1W	102.91 (7)	C1—C2—H2A	120.8
N1^i—Cu1—O1W	102.91 (7)	C2—C3—C4	119.6 (3)
N1—Cu1—N1^i	154.18 (13)	C2—C3—H3	120.2
O1A—Cl1—O2A	112.6 (6)	C4—C3—H3	120.2
O1A—Cl1—O3A	111.4 (6)	C3—C4—C5	119.7 (3)
O1A—Cl1—O4	110.9 (5)	C3—C4—H4	120.1
O1B—Cl1—O2B	99.4 (5)	C5—C4—H4	120.1
O1B—Cl1—O3B	117.1 (5)	N1—C5—C4	121.1 (3)
O1B—Cl1—O4	110.0 (5)	N1—C5—C6	118.7 (3)
O1C—Cl1—O2C	111.0 (9)	C4—C5—C6	120.2 (3)
O1C—Cl1—O3C	108.9 (12)	C5—C6—H6A	109.5
O1C—Cl1—O4	112.9 (12)	C5—C6—H6B	109.5
O2A—Cl1—O3A	103.4 (7)	H6A—C6—H6B	109.5
O2A—Cl1—O4	112.9 (7)	C5—C6—H6C	109.5
O3A—Cl1—O4	105.2 (5)	H6A—C6—H6C	109.5
O2B—Cl1—O3B	105.0 (5)	H6B—C6—H6C	109.5
O2B—Cl1—O4	105.3 (6)	O1—C7—N2	123.4 (3)
O3B—Cl1—O4	117.4 (4)	O1—C7—C8	120.1 (3)
O2C—Cl1—O3C	110.0 (11)	N2—C7—C8	116.5 (3)
O2C—Cl1—O4	101.5 (8)	C7—C8—H8A	109.5
O3C—Cl1—O4	112.3 (6)	C7—C8—H8B	109.5
C7—O1—Cu1	125.51 (19)	H8A—C8—H8B	109.5
C1—N1—C5	118.0 (2)	C7—C8—H8C	109.5
C1—N1—Cu1	120.43 (18)	H8A—C8—H8C	109.5
C5—N1—Cu1	121.18 (18)	H8B—C8—H8C	109.5
N1—C1—C2	122.8 (3)	Cu1—O1W—H1W	128 (2)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2A	0.81 (2)	1.96 (3)	2.731 (12)	157 (5)
O1W—H1W···O1C	0.81 (2)	2.06 (3)	2.83 (2)	160 (3)
N2—H2···O3A^ii	0.86	2.20	2.998 (10)	155
N2—H2···O3B^ii	0.86	2.17	2.971 (8)	155
N2—H2···O3C^ii	0.86	2.35	3.037 (15)	138

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