catena-Poly[[aquabis[N-(pyridin-3-yl)isonicotinamide-κN1]copper(II)]-μ-fumarato-κ2O1:O4]

Qiblawi, S.H.; LaDuca, R.L.

doi:10.1107/S1600536812047101

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page m1514

doi:10.1107/S1600536812047101

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catena-Poly[[aquabis[N-(pyridin-3-yl)isonicotinamide-κN¹]copper(II)]-μ-fumarato-κ²O¹:O⁴]

Sultan H. Qiblawi ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825 USA
^*Correspondence e-mail: laduca@msu.edu

(Received 13 November 2012; accepted 15 November 2012; online 24 November 2012)

In the title compound, [Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]_n, Cu^II ions on crystallographic twofold rotation axes are coordinated in a square pyramidal environment by two trans O atoms belonging to two monodentate fumarate anions, two trans isonicotinamide pyridyl N-donor atoms from monodentate, pendant 3-pyridylisonicotinamide (3-pina) ligands, and one apical aqua ligand, also sited on the crystallographic twofold rotation axis. The exobidentate fumarate ligands form [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chains that are arranged parallel to [001]. In the crystal, these polymeric chains are anchored into supramolecular layers parallel to (100) by O—H⋯O hydrogen bonds between aqua ligands and unligating fumarate O atoms, and N—H⋯O(=C) hydrogen bonds between 3-pina ligands. In turn, the layers aggregate by weak C—H⋯N and C—H⋯O hydrogen bonds, affording a three-dimensional network.

Related literature

For the preparation of 3-pyridylisonicotinamide, see: Gardner et al. (1954 ). For the preparation of other dicarboxylate coordination polymers containing 3-pyridylisonicotinamide, see: Kumar (2009 ).

Experimental

Crystal data

[Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]
M_r = 594.04
Monoclinic, C 2/c
a = 29.854 (4) Å
b = 5.3535 (7) Å
c = 17.353 (2) Å
β = 118.686 (2)°
V = 2433.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 173 K
0.25 × 0.13 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.794, T_max = 0.919
9406 measured reflections
2240 independent reflections
1758 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.083
S = 1.04
2240 reflections
188 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1ⁱ	0.84 (1)	1.83 (1)	2.660 (2)	169 (3)
N2—H2N⋯O2ⁱ	0.88 (2)	2.33 (2)	3.153 (3)	155 (3)
C2—H2⋯O4ⁱⁱ	0.95	2.48	3.360 (4)	153
C7—H7⋯O1ⁱⁱⁱ	0.95	2.48	3.430 (4)	178
C9—H9⋯N1^iv	0.95	2.39	3.263 (4)	153
C12—H12⋯O1^v	0.95	2.43	3.374 (4)	171
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (iii) $[-x, y+1, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x, -y+1, -z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812047101/lh5556sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047101/lh5556Isup2.hkl

checkCIF report

Comment top

In comparison to divalent metal coordination polymers containing rigid rod dipyridine ligands such as 4,4'-bipyridine, related materials containing the kinked dipodal ligand 3-pyridylisonicotinamide (3-pina) are much less common (Kumar, 2009). The title compound was obtained as blue crystals through the hydrothermal reaction of copper nitrate, fumaric acid, and 3-pina.

The asymmetric unit of the title compound contains a divalent copper atom and an aqua ligand on a crystallographic twofold rotation axis, a 3-pina ligand, and one half of a fumarate ligand whose centroid rests on a crystallographic inversion centre. The copper atom is square pyramidally coordinated (Fig. 1), with the basal plane containing trans isonicotinamide pyridyl N atom donors from two 3-pina ligands and trans O atom donors from monodentate carboxylate groups belonging to two fumarate ligands. The aqua ligand is located in the apical position.

The Cu atoms are linked by exobidentate, bis(monodentate) fumarate ligands to form [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chains that are oriented parallel to [0 0 1] (Fig. 2). Each individual chain is anchored to two others via O—H···O pairwise hydrogen bonding (Table 1) between aqua ligands and unligated fumarate O atoms, thereby constructing supramolecular two-dimensional layers arranged parallel to the bc crystal planes (Fig. 3). The stability of the layer motifs is enhanced by N—H···O hydrogen bonding between amide groups of adjacent 3-pina ligands (Fig. 4). In turn the layers stack along [1 0 0] in an AAA pattern via C—H···N interactions mediated by unligated 3-pyridyl N atoms belonging to the pendant 3-pina ligands (Fig. 5), thus forming the three-dimensional structure of the title compound which is also stabilized by weak C—H···O interactions.

Related literature top

For the preparation of 3-pyridylisonicotinamide, see: Gardner et al. (1954). For the preparation of other dicarboxylate coordination polymers containing 3-pyridylisonicotinamide, see: Kumar (2009).

Experimental top

Copper(II) nitrate hydrate and fumaric acid were obtained commercially. 3-Pyridylisonicotinamide (3-pina) was prepared via a published procedure (Gardner et al., 1954). A mixture of copper nitrate hydrate (86 mg, 0.37 mmol), fumaric acid (42 mg, 0.36 mmol), 3-pina (74 mg, 0.37 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr acid digestion bomb, which was then heated under autogenous pressure at 393 K for 24 h. Blue needles of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination environment of the title compound, showing 50% probability ellipsoids and atom numbering scheme. Hydrogen atom positions are shown as grey sticks. Color codes: dark blue Cu, red O, light blue N, black C, pink H. Symmetry code: (i) -x, y, -z + 1/2
	Fig. 2. A single [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chain.
	Fig. 3. Supramolecular layer of [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chains. O—H···O hydrogen bonding is shown as dashed lines.
	Fig. 4. Side view of the supramolecular layer of [Cu(fumarate)(3-pina)₂(H₂O)]_n coordination polymer chains. N—H···O hydrogen bonding between 3-pina amide groups is shown as dashed lines.
	Fig. 5. Stacking of supramolecular layers within the title compound.

catena-Poly[[aquabis[N-(pyridin-3-yl)isonicotinamide- κN¹]copper(II)]-µ-fumarato-κ²O¹:O⁴] top

Crystal data top

[Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]	F(000) = 1220
M_r = 594.04	D_x = 1.622 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3329 reflections
a = 29.854 (4) Å	θ = 2.7–25.3°
b = 5.3535 (7) Å	µ = 0.96 mm⁻¹
c = 17.353 (2) Å	T = 173 K
β = 118.686 (2)°	Needle, blue
V = 2433.0 (6) Å³	0.25 × 0.13 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2240 independent reflections
Radiation source: fine-focus sealed tube	1758 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω–ϕ scans	θ_max = 25.4°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −35→35
T_min = 0.794, T_max = 0.919	k = −6→6
9406 measured reflections	l = −20→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0303P)² + 4.2344P] where P = (F_o² + 2F_c²)/3
2240 reflections	(Δ/σ)_max < 0.001
188 parameters	Δρ_max = 0.34 e Å⁻³
5 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]	V = 2433.0 (6) Å³
M_r = 594.04	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 29.854 (4) Å	µ = 0.96 mm⁻¹
b = 5.3535 (7) Å	T = 173 K
c = 17.353 (2) Å	0.25 × 0.13 × 0.09 mm
β = 118.686 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2240 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1758 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.919	R_int = 0.053
9406 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	5 restraints
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.34 e Å⁻³
2240 reflections	Δρ_min = −0.36 e Å⁻³
188 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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.98462 (9)	0.2500	0.01332 (15)
O1	−0.01260 (9)	0.5988 (4)	0.10232 (13)	0.0329 (6)
O2	0.23784 (7)	0.6328 (4)	0.58520 (13)	0.0277 (5)
O3	0.0000	1.3863 (5)	0.2500	0.0288 (7)
H3O	−0.0035 (12)	1.471 (4)	0.2067 (12)	0.035*
O4	0.01923 (7)	0.9749 (3)	0.15746 (11)	0.0170 (4)
N1	0.34390 (10)	0.8621 (5)	0.83508 (17)	0.0384 (7)
N2	0.24546 (9)	1.0496 (5)	0.61401 (16)	0.0232 (6)
H2N	0.2343 (11)	1.199 (4)	0.5910 (18)	0.028*
N3	0.07405 (8)	0.9573 (4)	0.34350 (14)	0.0159 (5)
C1	0.37744 (12)	1.0459 (6)	0.8530 (2)	0.0344 (8)
H1	0.4076	1.0448	0.9083	0.041*
C2	0.37059 (12)	1.2372 (6)	0.7956 (2)	0.0339 (8)
H2	0.3955	1.3652	0.8108	0.041*
C3	0.32648 (12)	1.2391 (6)	0.7149 (2)	0.0295 (8)
H3	0.3203	1.3698	0.6739	0.035*
C4	0.30186 (11)	0.8643 (6)	0.75726 (19)	0.0292 (7)
H4	0.2777	0.7335	0.7438	0.035*
C5	0.29173 (10)	1.0479 (5)	0.69522 (18)	0.0201 (6)
C6	0.16993 (10)	0.8946 (5)	0.48796 (18)	0.0187 (6)
C7	0.09141 (10)	1.1150 (5)	0.41137 (18)	0.0199 (6)
H7	0.0702	1.2498	0.4094	0.024*
C8	0.15215 (10)	0.7307 (5)	0.41788 (18)	0.0195 (6)
H8	0.1725	0.5933	0.4188	0.023*
C9	0.13897 (10)	1.0906 (5)	0.48445 (18)	0.0214 (7)
H9	0.1502	1.2068	0.5315	0.026*
C10	0.10459 (10)	0.7686 (5)	0.34665 (18)	0.0193 (6)
H10	0.0930	0.6575	0.2981	0.023*
C11	0.00282 (10)	0.8103 (5)	0.09670 (18)	0.0180 (6)
C12	0.00079 (10)	0.8823 (5)	0.01221 (17)	0.0169 (6)
H12	0.0006	0.7540	−0.0257	0.020*
C13	0.22077 (10)	0.8447 (5)	0.56670 (18)	0.0205 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0147 (2)	0.0154 (3)	0.0090 (2)	0.000	0.00500 (19)	0.000
O1	0.0667 (16)	0.0171 (11)	0.0272 (12)	−0.0040 (11)	0.0324 (12)	−0.0003 (9)
O2	0.0219 (11)	0.0249 (12)	0.0250 (12)	0.0040 (9)	0.0022 (9)	0.0016 (10)
O3	0.058 (2)	0.0146 (16)	0.0144 (16)	0.000	0.0181 (16)	0.000
O4	0.0193 (10)	0.0222 (11)	0.0111 (9)	−0.0034 (8)	0.0086 (8)	−0.0021 (9)
N1	0.0373 (16)	0.0429 (18)	0.0212 (15)	−0.0081 (14)	0.0030 (13)	0.0075 (13)
N2	0.0191 (13)	0.0230 (15)	0.0187 (13)	0.0024 (11)	0.0020 (11)	0.0017 (11)
N3	0.0172 (12)	0.0188 (13)	0.0120 (11)	−0.0005 (10)	0.0073 (10)	−0.0011 (10)
C1	0.0261 (17)	0.043 (2)	0.0208 (16)	−0.0033 (15)	0.0005 (14)	−0.0006 (15)
C2	0.0243 (17)	0.035 (2)	0.0302 (19)	−0.0102 (14)	0.0033 (15)	−0.0011 (15)
C3	0.0307 (18)	0.0241 (18)	0.0255 (18)	−0.0030 (14)	0.0068 (15)	0.0037 (14)
C4	0.0262 (17)	0.0343 (19)	0.0206 (16)	−0.0115 (15)	0.0060 (14)	0.0012 (14)
C5	0.0144 (14)	0.0256 (17)	0.0171 (15)	0.0011 (12)	0.0050 (12)	−0.0024 (12)
C6	0.0153 (14)	0.0218 (15)	0.0169 (15)	0.0008 (12)	0.0060 (12)	0.0019 (12)
C7	0.0193 (15)	0.0225 (16)	0.0172 (15)	0.0030 (12)	0.0082 (12)	−0.0008 (13)
C8	0.0159 (14)	0.0199 (16)	0.0214 (16)	0.0017 (12)	0.0080 (13)	−0.0020 (12)
C9	0.0195 (15)	0.0234 (16)	0.0156 (15)	−0.0008 (12)	0.0040 (12)	−0.0076 (12)
C10	0.0223 (15)	0.0201 (16)	0.0158 (15)	−0.0008 (12)	0.0094 (13)	−0.0035 (12)
C11	0.0209 (15)	0.0160 (15)	0.0168 (15)	0.0057 (12)	0.0088 (12)	0.0027 (12)
C12	0.0215 (14)	0.0157 (13)	0.0154 (15)	−0.0008 (12)	0.0103 (12)	−0.0035 (12)
C13	0.0161 (14)	0.0241 (17)	0.0176 (15)	0.0023 (13)	0.0051 (12)	0.0020 (13)

Geometric parameters (Å, º) top

Cu1—O4ⁱ	1.9485 (17)	C2—C3	1.388 (4)
Cu1—O4	1.9485 (17)	C2—H2	0.9500
Cu1—N3	2.024 (2)	C3—C5	1.379 (4)
Cu1—N3ⁱ	2.024 (2)	C3—H3	0.9500
Cu1—O3	2.151 (3)	C4—C5	1.380 (4)
O1—C11	1.244 (3)	C4—H4	0.9500
O2—C13	1.222 (3)	C6—C9	1.380 (4)
O3—H3Oⁱ	0.839 (11)	C6—C8	1.382 (4)
O3—H3O	0.839 (11)	C6—C13	1.500 (4)
O4—C11	1.278 (3)	C7—C9	1.383 (4)
N1—C1	1.330 (4)	C7—H7	0.9500
N1—C4	1.331 (4)	C8—C10	1.378 (4)
N2—C13	1.356 (4)	C8—H8	0.9500
N2—C5	1.423 (3)	C9—H9	0.9500
N2—H2N	0.883 (17)	C10—H10	0.9500
N3—C7	1.335 (3)	C11—C12	1.489 (4)
N3—C10	1.344 (3)	C12—C12ⁱⁱ	1.323 (5)
C1—C2	1.374 (4)	C12—H12	0.9500
C1—H1	0.9500

O4ⁱ—Cu1—O4	176.95 (12)	N1—C4—C5	123.0 (3)
O4ⁱ—Cu1—N3	88.74 (8)	N1—C4—H4	118.5
O4—Cu1—N3	91.04 (8)	C5—C4—H4	118.5
O4ⁱ—Cu1—N3ⁱ	91.04 (8)	C3—C5—C4	118.6 (3)
O4—Cu1—N3ⁱ	88.74 (8)	C3—C5—N2	119.8 (3)
N3—Cu1—N3ⁱ	171.71 (13)	C4—C5—N2	121.5 (3)
O4ⁱ—Cu1—O3	91.52 (6)	C9—C6—C8	118.5 (2)
O4—Cu1—O3	91.52 (6)	C9—C6—C13	122.6 (3)
N3—Cu1—O3	94.15 (6)	C8—C6—C13	118.8 (2)
N3ⁱ—Cu1—O3	94.15 (6)	N3—C7—C9	122.8 (3)
H3Oⁱ—O3—Cu1	122.6 (17)	N3—C7—H7	118.6
H3Oⁱ—O3—H3O	115 (3)	C9—C7—H7	118.6
Cu1—O3—H3O	122.6 (17)	C10—C8—C6	119.4 (3)
C11—O4—Cu1	123.39 (17)	C10—C8—H8	120.3
C1—N1—C4	117.9 (3)	C6—C8—H8	120.3
C13—N2—C5	125.5 (2)	C6—C9—C7	118.9 (3)
C13—N2—H2N	119 (2)	C6—C9—H9	120.5
C5—N2—H2N	115 (2)	C7—C9—H9	120.5
C7—N3—C10	118.1 (2)	N3—C10—C8	122.3 (3)
C7—N3—Cu1	118.25 (18)	N3—C10—H10	118.9
C10—N3—Cu1	123.06 (18)	C8—C10—H10	118.9
N1—C1—C2	123.3 (3)	O1—C11—O4	125.0 (3)
N1—C1—H1	118.4	O1—C11—C12	118.1 (2)
C2—C1—H1	118.4	O4—C11—C12	116.9 (2)
C1—C2—C3	118.4 (3)	C12ⁱⁱ—C12—C11	122.7 (3)
C1—C2—H2	120.8	C12ⁱⁱ—C12—H12	118.6
C3—C2—H2	120.8	C11—C12—H12	118.6
C5—C3—C2	118.8 (3)	O2—C13—N2	123.7 (3)
C5—C3—H3	120.6	O2—C13—C6	121.1 (3)
C2—C3—H3	120.6	N2—C13—C6	115.2 (2)

O4ⁱ—Cu1—O3—H3Oⁱ	22 (3)	C13—N2—C5—C4	−36.8 (4)
O4—Cu1—O3—H3Oⁱ	−158 (3)	C10—N3—C7—C9	−0.6 (4)
N3—Cu1—O3—H3Oⁱ	−66 (3)	Cu1—N3—C7—C9	170.8 (2)
N3ⁱ—Cu1—O3—H3Oⁱ	114 (3)	C9—C6—C8—C10	0.6 (4)
N3—Cu1—O4—C11	121.8 (2)	C13—C6—C8—C10	177.4 (3)
N3ⁱ—Cu1—O4—C11	−49.9 (2)	C8—C6—C9—C7	0.3 (4)
O3—Cu1—O4—C11	−143.99 (19)	C13—C6—C9—C7	−176.4 (3)
O4ⁱ—Cu1—N3—C7	−50.8 (2)	N3—C7—C9—C6	−0.3 (4)
O4—Cu1—N3—C7	132.2 (2)	C7—N3—C10—C8	1.5 (4)
O3—Cu1—N3—C7	40.6 (2)	Cu1—N3—C10—C8	−169.4 (2)
O4ⁱ—Cu1—N3—C10	120.2 (2)	C6—C8—C10—N3	−1.5 (4)
O4—Cu1—N3—C10	−56.8 (2)	Cu1—O4—C11—O1	−24.5 (4)
O3—Cu1—N3—C10	−148.4 (2)	Cu1—O4—C11—C12	153.62 (18)
C4—N1—C1—C2	0.4 (5)	O1—C11—C12—C12ⁱⁱ	156.4 (3)
N1—C1—C2—C3	0.1 (5)	O4—C11—C12—C12ⁱⁱ	−21.9 (5)
C1—C2—C3—C5	−0.8 (5)	C5—N2—C13—O2	−6.2 (4)
C1—N1—C4—C5	−0.1 (5)	C5—N2—C13—C6	174.0 (2)
C2—C3—C5—C4	1.0 (5)	C9—C6—C13—O2	150.1 (3)
C2—C3—C5—N2	178.0 (3)	C8—C6—C13—O2	−26.5 (4)
N1—C4—C5—C3	−0.6 (5)	C9—C6—C13—N2	−30.1 (4)
N1—C4—C5—N2	−177.6 (3)	C8—C6—C13—N2	153.3 (3)
C13—N2—C5—C3	146.3 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1ⁱⁱⁱ	0.84 (1)	1.83 (1)	2.660 (2)	169 (3)
N2—H2N···O2ⁱⁱⁱ	0.88 (2)	2.33 (2)	3.153 (3)	155 (3)
C2—H2···O4^iv	0.95	2.48	3.360 (4)	153
C7—H7···O1^v	0.95	2.48	3.430 (4)	178
C9—H9···N1^vi	0.95	2.39	3.263 (4)	153
C12—H12···O1^vii	0.95	2.43	3.374 (4)	171

Symmetry codes: (iii) x, y+1, z; (iv) −x+1/2, −y+5/2, −z+1; (v) −x, y+1, −z+1/2; (vi) −x+1/2, y+1/2, −z+3/2; (vii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cu(C₄H₂O₄)(C₁₁H₉N₃O)₂(H₂O)]
M_r	594.04
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	29.854 (4), 5.3535 (7), 17.353 (2)
β (°)	118.686 (2)
V (Å³)	2433.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.25 × 0.13 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.794, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	9406, 2240, 1758
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.083, 1.04
No. of reflections	2240
No. of parameters	188
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Crystal Maker (Palmer, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1ⁱ	0.839 (11)	1.832 (10)	2.660 (2)	169 (3)
N2—H2N···O2ⁱ	0.883 (17)	2.33 (2)	3.153 (3)	155 (3)
C2—H2···O4ⁱⁱ	0.95	2.48	3.360 (4)	153
C7—H7···O1ⁱⁱⁱ	0.95	2.48	3.430 (4)	178
C9—H9···N1^iv	0.95	2.39	3.263 (4)	153
C12—H12···O1^v	0.95	2.43	3.374 (4)	171

Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, −y+5/2, −z+1; (iii) −x, y+1, −z+1/2; (iv) −x+1/2, y+1/2, −z+3/2; (v) −x, −y+1, −z.

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
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Kumar, D. K. (2009). Inorg. Chim. Acta, 362, 1767–1771. Web of Science CSD CrossRef Google Scholar
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Sheldrick, G. M. (1996). SADABS, University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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