(Di-2-pyridyl­amine)­(methanol)sulfato­copper(II)

DeBurgomaster, P.; Zubieta, J.

doi:10.1107/S1600536810038675

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages m1350-m1351

https://doi.org/10.1107/S1600536810038675

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(Di-2-pyridylamine)(methanol)sulfatocopper(II)

Paul DeBurgomaster ^a and Jon Zubieta ^a ^*

^aDepartment of Chemistry, Syracuse University, Syracuse, New York 13244, USA
^*Correspondence e-mail: jazubiet@syr.edu

(Received 20 September 2010; accepted 27 September 2010; online 2 October 2010)

The title complex, [Cu(SO₄)(C₁₀H₉N₃)(CH₃OH)], is a mononuclear species with the Cu^II ion in a Jahn–Teller-distorted `4 + 1' square-pyramidal geometry. The basal plane is defined by the pyridyl N-atom donors of the bipyridylamine (bpa) ligand and two O-atom donors of the sulfate ligand. The coordination geometry is completed by the axial coordination of a methanol O-atom donor. The axial bond length displays the usual elongation: Cu—O(axial) = 2.168 (2), Cu—O(basal) = 2.016 (2) (average) and Cu—N(basal) = 1.951 (3) Å (average). In the crystal structure, the complex molecules are linked through N—H⋯O and O—H⋯O hydrogen bonds into chains along [100].

Related literature

For structures of other copper-bis(2-pyridyl)amine complexes, see: Fischer & Bau (1977 ); Kavounis et al. (1999 ); Youngme et al. (2005 ). For solvatothermal chemistry of compounds containing copper-bis(2-pyridyl)amine subunits, see: DeBurgomaster et al. (2010 ). For structural chemistry of the related tridentate ligand bis(2-pyridylmethyl)amine, see: Bartholomä et al. (2010a , b ,c ,d ,e ). For copper–pyridyl subunits in the design of organic–inorganic hybrid materials, see: Armatas et al. (2005 ); Chesnut et al. (1999 ); Hagrman et al. (1999 ).

Experimental

Crystal data

[Cu(SO₄)(C₁₀H₉N₃)(CH₄O)]
M_r = 362.84
Monoclinic, P 2₁ /n
a = 7.1403 (10) Å
b = 10.7361 (15) Å
c = 17.798 (3) Å
β = 92.185 (3)°
V = 1363.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.78 mm⁻¹
T = 90 K
0.30 × 0.15 × 0.07 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.617, T_max = 0.886
13215 measured reflections
3308 independent reflections
3119 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.109
S = 1.26
3308 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—HN2⋯O3ⁱ	0.90	1.97	2.854 (3)	169
O5—HO5⋯O3ⁱⁱ	0.89	1.82	2.700 (3)	168
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810038675/hg2716sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038675/hg2716Isup2.hkl

checkCIF report

Comment top

In the course of our investigations of the design of materials constructed from metal oxide nodes linked through or decorated with copper-pyridyl subunits (Armatas et al. (2005); Chesnut et al. (1999); Hagrman et al. (1999)), we prepared and investigated a series of dipodal ligands with bis(2-pyridylmethyl)amine termini (Bartholomä et al. (2010a,b,c,d,e). Since this ligand acts as a tridentate donor, the structural consequences of introducing an analogous bidentate ligand, such as bis(2-pyridyl)amine were of interest in expanding the structural data base. Representative examples of copper-bis(2-pyridyl)amine complexes have been reported (Fischer & Bau (1977); Kavounis et al. (1999); Youngme et al. (2005)), as well as {Cu(bpa)}²⁺ subunits in metal oxide complexes (DeBurgomaster et al. (2010)). As shown in Fig. 1, the mononuclear complex exhibits copper(II) sites in a distorted '4 + 1' square pyramidal geometry. The basal plane is defined by the pyridyl nitrogen donors of the bis(2-pyridyl)amine ligand and two sulfato oxygen donors, while the apical position is occupied by the oxygen donor of the methanol ligand. The bond lengths demonstrate the lengthening of the axial Cu—O bond with respect to the bonds in the basal plane: Cu—N1, 1.946 (3) Å; Cu—N2, 1.955 (3) Å; Cu—O1, 2.004 (2) Å; Cu—O2, 2.027 (2) Å; Cu—O5, 2.168 (2) Å. The structure is stabilized by intermolecular hydrogen-bonding between the amine N—H group and a pendant sulfate oxygen and between the methanol O—H group and the pendant sulfate oxygen (Fig. 2). This results in a one-dimensional hydrogen-bonded double chain parallel to the [100] direction (Fig. 3).

Related literature top

For structures of other copper-bis(2-pyridyl)amine complexes, see: Fischer & Bau (1977); Kavounis et al. (1999); Youngme et al. (2005). For solvatothermal chemistry of compounds containing copper-bis(2-pyridyl)amine subunits, see: DeBurgomaster et al. (2010). For structural chemistry of the related tridentate ligand bis(2-pyridylmethyl)amine, see: Bartholomä et al. (2010a, b,c,d,e). For copper–pyridyl subunits in the design of organic–inorganic hybrid materials, see: Armatas et al. (2005); Chesnut et al. (1999); Hagrman et al. (1999).

Experimental top

Synthesis of [Cu(SO₄)(C₁₀H₉N₃)(CH₃OH)]. A solution of Cu(SO₄).5H2O (0.250 g, 1.0 mmol) and bis(2-pyridyl)amine (0.171 g, 1.0 mmol) in 10 ml of methanol was heated to 75° C for 48 h (initial and final pH, 4.0). Blue crystals of the product were isolated in 25% yield. Anal. Calcd. for C₁₁H₁₃CuN₃O₅S: C, 36.4; H, 3.58; N, 11.6. Found: C, 36.2; H, 3.69; N, 11.5.

Structure description top

For structures of other copper-bis(2-pyridyl)amine complexes, see: Fischer & Bau (1977); Kavounis et al. (1999); Youngme et al. (2005). For solvatothermal chemistry of compounds containing copper-bis(2-pyridyl)amine subunits, see: DeBurgomaster et al. (2010). For structural chemistry of the related tridentate ligand bis(2-pyridylmethyl)amine, see: Bartholomä et al. (2010a, b,c,d,e). For copper–pyridyl subunits in the design of organic–inorganic hybrid materials, see: Armatas et al. (2005); Chesnut et al. (1999); Hagrman et al. (1999).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP view of the structure of the title complex, showing displacement ellipsoids at the 50% probability level and the atom-labeling scheme. The pyridyl group hydrogen atoms have been omitted for clarity.
	Fig. 2. A view of the packing in the bc plane.
	Fig. 3. A view of the hydrogen-bonded double chains running parallel to [100]. The hydrogen bonds are shown as red and green multiband cylinders.

(Di-2-pyridylamine)(methanol)sulfatocopper(II) top

Crystal data top

[Cu(SO₄)(C₁₀H₉N₃)(CH₄O)]	F(000) = 740
M_r = 362.84	D_x = 1.768 Mg m⁻³ D_m = 1.75 (2) Mg m⁻³ D_m measured by flotation
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4522 reflections
a = 7.1403 (10) Å	θ = 3.0–28.3°
b = 10.7361 (15) Å	µ = 1.78 mm⁻¹
c = 17.798 (3) Å	T = 90 K
β = 92.185 (3)°	Plate, green
V = 1363.4 (3) Å³	0.30 × 0.15 × 0.07 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	3308 independent reflections
Radiation source: fine-focus sealed tube	3119 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 512 pixels mm^-1	θ_max = 28.1°, θ_min = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −14→13
T_min = 0.617, T_max = 0.886	l = −23→23
13215 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.26	w = 1/[σ²(F_o²) + (0.0374P)² + 3.5736P] where P = (F_o² + 2F_c²)/3
3308 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

[Cu(SO₄)(C₁₀H₉N₃)(CH₄O)]	V = 1363.4 (3) Å³
M_r = 362.84	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1403 (10) Å	µ = 1.78 mm⁻¹
b = 10.7361 (15) Å	T = 90 K
c = 17.798 (3) Å	0.30 × 0.15 × 0.07 mm
β = 92.185 (3)°

Data collection top

Bruker APEX CCD area-detector diffractometer	3308 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3119 reflections with I > 2σ(I)
T_min = 0.617, T_max = 0.886	R_int = 0.033
13215 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.26	Δρ_max = 0.79 e Å⁻³
3308 reflections	Δρ_min = −0.75 e Å⁻³
192 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	0.64877 (5)	0.27906 (3)	0.05295 (2)	0.00870 (12)
S1	0.37436 (10)	0.16887 (7)	0.11547 (4)	0.00900 (16)
O1	0.4394 (3)	0.1566 (2)	0.03641 (12)	0.0116 (4)
O2	0.5310 (3)	0.2441 (2)	0.15261 (13)	0.0118 (5)
O3	0.2005 (3)	0.2444 (2)	0.11458 (13)	0.0131 (5)
O4	0.3483 (3)	0.0501 (2)	0.15113 (13)	0.0138 (5)
O5	0.8729 (3)	0.1433 (2)	0.06432 (14)	0.0174 (5)
HO5	0.9887	0.1690	0.0770	0.029 (12)*
N1	0.6684 (4)	0.3176 (2)	−0.05332 (15)	0.0100 (5)
N2	0.7276 (4)	0.5328 (2)	−0.03312 (15)	0.0111 (5)
HN2	0.7638	0.5982	−0.0606	0.017 (10)*
N3	0.7710 (4)	0.4339 (2)	0.08540 (15)	0.0105 (5)
C1	0.6369 (4)	0.2227 (3)	−0.10237 (18)	0.0134 (6)
H1	0.6295	0.1404	−0.0832	0.016*
C2	0.6153 (5)	0.2405 (3)	−0.17841 (19)	0.0144 (6)
H2	0.5978	0.1717	−0.2115	0.017*
C3	0.6197 (5)	0.3619 (3)	−0.20600 (19)	0.0152 (7)
H3	0.5984	0.3774	−0.2582	0.018*
C4	0.6550 (4)	0.4588 (3)	−0.15736 (19)	0.0129 (6)
H4	0.6601	0.5419	−0.1755	0.015*
C5	0.6835 (4)	0.4337 (3)	−0.08069 (18)	0.0103 (6)
C6	0.7789 (4)	0.5367 (3)	0.04263 (18)	0.0106 (6)
C7	0.8364 (5)	0.6517 (3)	0.07262 (19)	0.0147 (6)
H7	0.8393	0.7236	0.0415	0.018*
C8	0.8885 (5)	0.6594 (3)	0.1477 (2)	0.0169 (7)
H8	0.9272	0.7367	0.1691	0.020*
C9	0.8838 (5)	0.5519 (3)	0.19230 (19)	0.0166 (7)
H9	0.9213	0.5546	0.2441	0.020*
C10	0.8242 (4)	0.4435 (3)	0.15956 (18)	0.0138 (6)
H10	0.8194	0.3709	0.1899	0.017*
C11	0.8502 (5)	0.0179 (3)	0.0901 (2)	0.0208 (8)
H11A	0.9712	−0.0252	0.0903	0.031*
H11B	0.7603	−0.0258	0.0565	0.031*
H11C	0.8036	0.0189	0.1412	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00907 (19)	0.00779 (19)	0.00915 (19)	−0.00177 (14)	−0.00090 (13)	0.00045 (14)
S1	0.0095 (3)	0.0083 (3)	0.0091 (3)	−0.0007 (3)	−0.0005 (3)	0.0008 (3)
O1	0.0126 (11)	0.0117 (11)	0.0104 (10)	−0.0052 (8)	−0.0002 (8)	−0.0010 (9)
O2	0.0124 (11)	0.0116 (11)	0.0114 (10)	−0.0031 (8)	−0.0018 (8)	−0.0003 (8)
O3	0.0119 (11)	0.0087 (10)	0.0187 (12)	0.0012 (8)	0.0000 (9)	0.0031 (9)
O4	0.0200 (12)	0.0067 (10)	0.0145 (11)	−0.0010 (9)	−0.0005 (9)	0.0022 (9)
O5	0.0122 (11)	0.0119 (11)	0.0277 (13)	−0.0005 (9)	−0.0028 (10)	0.0031 (10)
N1	0.0094 (12)	0.0096 (12)	0.0112 (12)	−0.0001 (10)	0.0022 (9)	−0.0007 (10)
N2	0.0131 (13)	0.0064 (12)	0.0138 (13)	−0.0013 (10)	−0.0010 (10)	0.0018 (10)
N3	0.0093 (12)	0.0098 (12)	0.0122 (13)	−0.0012 (10)	−0.0015 (10)	0.0004 (10)
C1	0.0146 (15)	0.0093 (14)	0.0163 (16)	−0.0012 (12)	0.0010 (12)	−0.0021 (12)
C2	0.0167 (16)	0.0125 (15)	0.0139 (15)	−0.0004 (12)	0.0008 (12)	−0.0046 (12)
C3	0.0142 (15)	0.0210 (17)	0.0107 (15)	0.0017 (13)	0.0026 (12)	0.0012 (13)
C4	0.0139 (15)	0.0089 (14)	0.0160 (16)	0.0001 (12)	0.0020 (12)	0.0019 (12)
C5	0.0067 (13)	0.0112 (14)	0.0132 (15)	0.0016 (11)	0.0013 (11)	−0.0023 (12)
C6	0.0063 (13)	0.0124 (15)	0.0132 (15)	0.0002 (11)	0.0004 (11)	0.0004 (12)
C7	0.0153 (16)	0.0093 (15)	0.0191 (16)	0.0007 (12)	−0.0033 (12)	0.0016 (13)
C8	0.0139 (16)	0.0155 (16)	0.0211 (17)	−0.0030 (13)	−0.0031 (13)	−0.0071 (14)
C9	0.0130 (15)	0.0227 (18)	0.0137 (16)	−0.0006 (13)	−0.0044 (12)	−0.0014 (13)
C10	0.0125 (15)	0.0166 (16)	0.0119 (15)	−0.0030 (12)	−0.0022 (12)	0.0028 (12)
C11	0.0171 (17)	0.0091 (16)	0.036 (2)	0.0005 (13)	−0.0048 (15)	0.0021 (14)

Geometric parameters (Å, º) top

Cu1—N1	1.946 (3)	C1—H1	0.9500
Cu1—N3	1.955 (3)	C2—C3	1.394 (5)
Cu1—O1	2.004 (2)	C2—H2	0.9500
Cu1—O2	2.027 (2)	C3—C4	1.370 (5)
Cu1—O5	2.168 (2)	C3—H3	0.9500
S1—O4	1.439 (2)	C4—C5	1.398 (5)
S1—O3	1.482 (2)	C4—H4	0.9500
S1—O1	1.504 (2)	C6—C7	1.401 (4)
S1—O2	1.511 (2)	C7—C8	1.375 (5)
O5—C11	1.434 (4)	C7—H7	0.9500
O5—HO5	0.8923	C8—C9	1.402 (5)
N1—C5	1.343 (4)	C8—H8	0.9500
N1—C1	1.355 (4)	C9—C10	1.363 (5)
N2—C6	1.384 (4)	C9—H9	0.9500
N2—C5	1.389 (4)	C10—H10	0.9500
N2—HN2	0.8988	C11—H11A	0.9800
N3—C6	1.343 (4)	C11—H11B	0.9800
N3—C10	1.363 (4)	C11—H11C	0.9800
C1—C2	1.369 (5)

N1—Cu1—N3	93.33 (11)	C1—C2—C3	118.4 (3)
N1—Cu1—O1	94.47 (10)	C1—C2—H2	120.8
N3—Cu1—O1	157.45 (10)	C3—C2—H2	120.8
N1—Cu1—O2	159.62 (10)	C4—C3—C2	119.6 (3)
N3—Cu1—O2	95.43 (10)	C4—C3—H3	120.2
O1—Cu1—O2	71.02 (9)	C2—C3—H3	120.2
N1—Cu1—O5	98.83 (10)	C3—C4—C5	119.1 (3)
N3—Cu1—O5	102.96 (10)	C3—C4—H4	120.4
O1—Cu1—O5	96.70 (9)	C5—C4—H4	120.4
O2—Cu1—O5	97.08 (9)	N1—C5—N2	120.6 (3)
O4—S1—O3	111.51 (14)	N1—C5—C4	121.5 (3)
O4—S1—O1	112.62 (14)	N2—C5—C4	117.9 (3)
O3—S1—O1	109.03 (13)	N3—C6—N2	120.8 (3)
O4—S1—O2	112.73 (14)	N3—C6—C7	121.8 (3)
O3—S1—O2	108.55 (13)	N2—C6—C7	117.4 (3)
O1—S1—O2	101.91 (13)	C8—C7—C6	119.2 (3)
S1—O1—Cu1	93.46 (11)	C8—C7—H7	120.4
S1—O2—Cu1	92.35 (11)	C6—C7—H7	120.4
C11—O5—Cu1	124.7 (2)	C7—C8—C9	119.3 (3)
C11—O5—HO5	108.9	C7—C8—H8	120.3
Cu1—O5—HO5	119.3	C9—C8—H8	120.3
C5—N1—C1	118.5 (3)	C10—C9—C8	118.3 (3)
C5—N1—Cu1	124.0 (2)	C10—C9—H9	120.8
C1—N1—Cu1	116.7 (2)	C8—C9—H9	120.8
C6—N2—C5	131.5 (3)	C9—C10—N3	123.3 (3)
C6—N2—HN2	115.8	C9—C10—H10	118.3
C5—N2—HN2	109.2	N3—C10—H10	118.3
C6—N3—C10	118.1 (3)	O5—C11—H11A	109.5
C6—N3—Cu1	124.0 (2)	O5—C11—H11B	109.5
C10—N3—Cu1	117.0 (2)	H11A—C11—H11B	109.5
N1—C1—C2	122.8 (3)	O5—C11—H11C	109.5
N1—C1—H1	118.6	H11A—C11—H11C	109.5
C2—C1—H1	118.6	H11B—C11—H11C	109.5

O4—S1—O1—Cu1	−130.74 (12)	N1—Cu1—N3—C10	−168.3 (2)
O3—S1—O1—Cu1	104.93 (12)	O1—Cu1—N3—C10	81.6 (4)
O2—S1—O1—Cu1	−9.70 (13)	O2—Cu1—N3—C10	30.1 (2)
N1—Cu1—O1—S1	−157.87 (12)	O5—Cu1—N3—C10	−68.4 (2)
N3—Cu1—O1—S1	−48.0 (3)	C5—N1—C1—C2	−1.6 (5)
O2—Cu1—O1—S1	7.46 (10)	Cu1—N1—C1—C2	168.9 (3)
O5—Cu1—O1—S1	102.68 (12)	N1—C1—C2—C3	−2.2 (5)
O4—S1—O2—Cu1	130.54 (12)	C1—C2—C3—C4	3.4 (5)
O3—S1—O2—Cu1	−105.41 (12)	C2—C3—C4—C5	−0.8 (5)
O1—S1—O2—Cu1	9.58 (13)	C1—N1—C5—N2	−175.8 (3)
N1—Cu1—O2—S1	39.0 (3)	Cu1—N1—C5—N2	14.4 (4)
N3—Cu1—O2—S1	154.08 (12)	C1—N1—C5—C4	4.3 (4)
O1—Cu1—O2—S1	−7.42 (10)	Cu1—N1—C5—C4	−165.4 (2)
O5—Cu1—O2—S1	−102.10 (11)	C6—N2—C5—N1	6.5 (5)
N1—Cu1—O5—C11	−122.5 (3)	C6—N2—C5—C4	−173.6 (3)
N3—Cu1—O5—C11	141.9 (3)	C3—C4—C5—N1	−3.1 (5)
O1—Cu1—O5—C11	−26.9 (3)	C3—C4—C5—N2	177.0 (3)
O2—Cu1—O5—C11	44.7 (3)	C10—N3—C6—N2	179.7 (3)
N3—Cu1—N1—C5	−24.1 (3)	Cu1—N3—C6—N2	−11.3 (4)
O1—Cu1—N1—C5	134.7 (3)	C10—N3—C6—C7	−1.1 (4)
O2—Cu1—N1—C5	91.3 (4)	Cu1—N3—C6—C7	167.9 (2)
O5—Cu1—N1—C5	−127.8 (2)	C5—N2—C6—N3	−8.2 (5)
N3—Cu1—N1—C1	166.0 (2)	C5—N2—C6—C7	172.6 (3)
O1—Cu1—N1—C1	−35.2 (2)	N3—C6—C7—C8	0.8 (5)
O2—Cu1—N1—C1	−78.6 (4)	N2—C6—C7—C8	−180.0 (3)
O5—Cu1—N1—C1	62.3 (2)	C6—C7—C8—C9	0.4 (5)
N1—Cu1—N3—C6	22.6 (3)	C7—C8—C9—C10	−1.2 (5)
O1—Cu1—N3—C6	−87.5 (4)	C8—C9—C10—N3	0.9 (5)
O2—Cu1—N3—C6	−139.0 (3)	C6—N3—C10—C9	0.3 (5)
O5—Cu1—N3—C6	122.4 (2)	Cu1—N3—C10—C9	−169.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···O3ⁱ	0.90	1.97	2.854 (3)	169
O5—HO5···O3ⁱⁱ	0.89	1.82	2.700 (3)	168

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

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₁₀H₉N₃)(CH₄O)]
M_r	362.84
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	90
a, b, c (Å)	7.1403 (10), 10.7361 (15), 17.798 (3)
β (°)	92.185 (3)
V (Å³)	1363.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.78
Crystal size (mm)	0.30 × 0.15 × 0.07

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.617, 0.886
No. of measured, independent and observed [I > 2σ(I)] reflections	13215, 3308, 3119
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.109, 1.26
No. of reflections	3308
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.75

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···O3ⁱ	0.90	1.97	2.854 (3)	169.3
O5—HO5···O3ⁱⁱ	0.89	1.82	2.700 (3)	168.4

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

Acknowledgements

This work was supported by a grant from the National Science Foundation, CHE-0907787.

References

Armatas, G. N., Burkholder, E. & Zubieta, J. (2005). J. Solid State Chem. 718, 2430–2435. Google Scholar
Bartholomä, M., Cheung, H., Darling, K. & Zubieta, J. (2010e). Acta Cryst. E66, m1201–m1202. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010a). Acta Cryst. E66, m1195–m1196. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010b). Acta Cryst. E66, m1197. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010c). Acta Cryst. E66, m1198. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bartholomä, M., Cheung, H. & Zubieta, J. (2010d). Acta Cryst. E66, m1199–m1200. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Chesnut, D. J., Hagrman, D., Zapf, P. J., Hammond, R. P., LaDuca, R., Haushalter, R. C. & Zubieta, J. (1999). Coord. Chem. Rev. 190–192, 737–769. CrossRef CAS Google Scholar
DeBurgomaster, P., Bartholoma, M., Raffel, R., Ouellette, W., Muller, A. & Zubieta, J. (2010). Inorg. Chim. Acta, 63, 1386–1394. Web of Science CSD CrossRef Google Scholar
Fischer, B. E. & Bau, R. (1977). J. Chem. Soc. Chem. Commun. pp. 272–273. CrossRef Web of Science Google Scholar
Hagrman, P. J., Hagrman, D. & Zubieta, J. (1999). Angew. Chem. Int. Ed. 38, 2638–2684. CrossRef Google Scholar
Kavounis, C. A., Tzavellas, C., Cardin, C. J. & Zubavichus, Y. (1999). Struct. Chem. 10, 411–417. Web of Science CSD CrossRef CAS Google Scholar
Palmer, D. (2006). Crystal Maker. Crystal Maker Software Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Youngme, S., Phuengphai, P., Pakawatchai, C., Van Albada, G. A. & Reedijk, J. (2005). Inorg. Chim. Acta, 358, 2125–2128. Web of Science CSD CrossRef CAS Google Scholar