(Di-2-pyridyl-amine)-(methanol)sulfato-copper(II).

The title complex, [Cu(SO(4))(C(10)H(9)N(3))(CH(3)OH)], 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 bipyridyl-amine (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 mol-ecules 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 = 362.84

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.109

S = 1.26

3308 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.75 e Å−3

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 ▶).

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038675/hg2716Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(SO4)(C10H9N3)(CH4O)]	F(000) = 740
Mr = 362.84	Dx = 1.768 Mg m−3Dm = 1.75 (2) Mg m−3Dm 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

Bruker APEX CCD area-detector diffractometer	3308 independent reflections
Radiation source: fine-focus sealed tube	3119 reflections with I > 2σ(I)
graphite	Rint = 0.033
Detector resolution: 512 pixels mm-1	θmax = 28.1°, θmin = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −14→13
Tmin = 0.617, Tmax = 0.886	l = −23→23
13215 measured reflections

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(Fo2) + (0.0374P)2 + 3.5736P] where P = (Fo2 + 2Fc2)/3
3308 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.79 e Å−3
0 restraints	Δρmin = −0.75 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) ; (ii) .