Aqua­[1-(1,10-phenanthrolin-2-yl-κ2N,N′)-1H-pyrazol-3-amine-κN2](sulfato-κO)copper(II) methanol monosolvate dihydrate

Yuan, L.; Lian, L.S.; Hui, C.Y.; Xia, Z.Y.; Min, S.J.

doi:10.1107/S1600536812014134

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m558-m559

doi:10.1107/S1600536812014134

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Aqua[1-(1,10-phenanthrolin-2-yl-κ²N,N′)-1H-pyrazol-3-amine-κN²](sulfato-κO)copper(II) methanol monosolvate dihydrate

Liang Yuan,^a Liu Shu Lian,^b Chi Yan Hui,^a Zhao Yan Xia ^c and Shi Jing Min ^a ^*

^aCollege of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan 250014, People's Republic of China, ^bSchool for Cadres of Shandong Bureau of Quality and Technical Supervision, Jinan 250014, People's Republic of China, and ^cShandong Academy of Medical Science Graduate Education Center, Jinan 250062, People's Republic of China
^*Correspondence e-mail: shijingmin1955@gmail.com

(Received 12 March 2012; accepted 1 April 2012; online 13 April 2012)

In the title compound, [Cu(SO₄)(C₁₅H₁₁N₅)(H₂O)]·CH₃OH·2H₂O, the Cu^II ion is in a distorted square-pyramidal geometry, in which three N atoms from the chelating 1-(1,10-phenanthrolin-2-yl)-1H-pyrazol-3-amine ligand and one O atom from a sulfate anion define the basal plane and the O atom from the coordinating water molecule is located at the apex. In the crystal, hydrogen-bonding interactions involving the coordinating and solvent water molecules, the methanol solvent molecule and the amine group (one with an intramolecular interaction to one of the sulfate O atoms) of the complex are observed. π–π interactions between symmetry-related phenantroline moieties, with a shortest centroid–centroid interaction of 3.573 (2)°, are also present.

Related literature

For related structures, see: Li et al. (2011a ,b ).

Experimental

Crystal data

[Cu(SO₄)(C₁₅H₁₁N₅)(H₂O)]·CH₄O·2H₂O
M_r = 506.98
Monoclinic, P 2₁ /n
a = 8.0190 (13) Å
b = 18.489 (3) Å
c = 14.086 (2) Å
β = 104.551 (2)°
V = 2021.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 298 K
0.22 × 0.15 × 0.11 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.772, T_max = 0.876
11702 measured reflections
4394 independent reflections
3434 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.119
S = 1.03
4394 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O3	1.906 (2)
Cu1—N2	1.934 (2)
Cu1—N3	2.068 (2)
Cu1—N1	2.090 (2)
Cu1—O5	2.220 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H4⋯O7	0.89	1.79	2.671 (4)	167
O5—H5⋯O8	0.89	1.90	2.774 (4)	164
O6—H12⋯O1	0.85	1.89	2.668 (4)	152
O7—H6⋯O6	0.84	2.10	2.878 (5)	153
O7—H7⋯O4ⁱ	0.89	1.84	2.726 (4)	173
O8—H17⋯O6ⁱⁱ	0.90	2.07	2.906 (5)	154
O8—H18⋯O2ⁱⁱⁱ	0.90	2.09	2.957 (4)	163
N5—H5A⋯O4	0.86	2.19	2.916 (4)	143
N5—H5B⋯O2ⁱⁱ	0.86	2.17	3.022 (4)	175
Symmetry codes: (i) x-1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 200 ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014134/wm2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014134/wm2604Isup2.hkl

checkCIF report

Comment top

Derivatives of 1,10-phenanthroline play an important role in coordination chemistry and many of such complexes have been reported with these types of derivatives as ligands, e.g. Li et al. (2011a,b) for closely related Cu^II complexes. To the best of our knowledge, there is no report for a complex with 1-(1,10-phenanthrolin-9-yl)-1H-pyrazol-3-amine as ligand. Herein we report the crystal of the solvated title complex, (I).

The molecular structure of (I) is shown in Fig. 1. The Cu^II ion is is a distorted square-pyramidal coordination geometry with the O atom of the water molecule at the apex and three N atoms from the ligand and one O atoms from the sulfate anion in the basal plane. The non-hydrogen atoms from the 1-(1,10-phenanthrolin-9-yl)-1H-pyrazol-3-amine ligand make an approximate plane within 0.074 Å (rms deviation) with a maximum deviation of 0.145 (3) Å for the N5 atom.

In the crystal, the uncoordinated water molecules, the methanol molecule and the metal complex are connected to each other by hydrogen bonding interactions as shown in Table 2 and Figure 2. The coordinating water molecule and the solvent water molecule (O5—H4···O7 and O5—H5···O8) interact, as well as the solvent water molecules with the methanol molecule (O7—H6···O6 and O8—H17···O6). The solvent water molecules are also donors to the free sulfate O atoms of the complex (O7—H7···O4; O8—H18···O2). The complex is also connected via its amine function as donor molecule to an the adjacent complex (N5—H5···O2).There is also an intramolecular hydrogen bond in the complex, which involves the amine group and the O atom from sulfate anion (N5—H5A···O4).

π—π interactions between symmetry-related phenantroline moieties with a shortest centroid to centroid interaction of 3.573 (2) Å may consolidate the crystal packing.

Related literature top

For related structures, see: Li et al. (2011a,b).

Experimental top

A 10 mL methanol solution of 1-(1,10-phenanthrolin-9-yl)-1H-pyrazol-3-amine (0.0549 g, 0.21 mmol) was added into a 10 mL water solution containing CuSO₄^.5H₂O (0.0549 g, 0.22 mmol), and the resulting solution was stirred for a few minutes. Yellow single crystals were obtained after the filtrate had been allowed to stand at room temperature for about one week.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids shown at the 30% probability level.
	Fig. 2. Unit cell of (I), showing the packing features consolidated by hydrogen bonding interactions

Aqua[1-(1,10-phenanthrolin-2-yl-κ²N,N')-1H-pyrazol-3- amine-κN²](sulfato-κO)copper(II) methanol monosolvate dihydrate top

Crystal data top

[Cu(SO₄)(C₁₅H₁₁N₅)(H₂O)]·CH₄O·2H₂O	F(000) = 1044
M_r = 506.98	D_x = 1.666 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2683 reflections
a = 8.0190 (13) Å	θ = 2.7–23.6°
b = 18.489 (3) Å	µ = 1.24 mm⁻¹
c = 14.086 (2) Å	T = 298 K
β = 104.551 (2)°	Prism, yellow
V = 2021.4 (6) Å³	0.22 × 0.15 × 0.11 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4394 independent reflections
Radiation source: fine-focus sealed tube	3434 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→7
T_min = 0.772, T_max = 0.876	k = −23→19
11702 measured reflections	l = −17→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0628P)² + 0.2654P] where P = (F_o² + 2F_c²)/3
4394 reflections	(Δ/σ)_max = 0.001
281 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cu(SO₄)(C₁₅H₁₁N₅)(H₂O)]·CH₄O·2H₂O	V = 2021.4 (6) Å³
M_r = 506.98	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.0190 (13) Å	µ = 1.24 mm⁻¹
b = 18.489 (3) Å	T = 298 K
c = 14.086 (2) Å	0.22 × 0.15 × 0.11 mm
β = 104.551 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	4394 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3434 reflections with I > 2σ(I)
T_min = 0.772, T_max = 0.876	R_int = 0.038
11702 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.03	Δρ_max = 0.52 e Å⁻³
4394 reflections	Δρ_min = −0.31 e Å⁻³
281 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1583 (4)	0.18352 (19)	−0.0328 (3)	0.0448 (8)
H1	0.1747	0.2313	−0.0121	0.054*
C2	0.0344 (5)	0.1677 (2)	−0.1206 (3)	0.0554 (10)
H2	−0.0272	0.2050	−0.1579	0.066*
C3	0.0052 (5)	0.0986 (2)	−0.1506 (3)	0.0541 (10)
H3	−0.0761	0.0883	−0.2088	0.065*
C4	0.0969 (4)	0.04186 (19)	−0.0944 (2)	0.0423 (8)
C5	0.2197 (4)	0.06290 (17)	−0.0093 (2)	0.0353 (7)
C6	0.3202 (4)	0.00945 (16)	0.0501 (2)	0.0352 (7)
C7	0.3036 (4)	−0.06449 (17)	0.0284 (3)	0.0427 (8)
C8	0.1765 (5)	−0.0840 (2)	−0.0580 (3)	0.0532 (10)
H8	0.1609	−0.1326	−0.0749	0.064*
C9	0.0787 (5)	−0.0343 (2)	−0.1156 (3)	0.0532 (10)
H9	−0.0036	−0.0495	−0.1710	0.064*
C10	0.4149 (5)	−0.11097 (18)	0.0962 (3)	0.0506 (9)
H10	0.4066	−0.1607	0.0860	0.061*
C11	0.5327 (5)	−0.08488 (17)	0.1751 (3)	0.0475 (9)
H11	0.6048	−0.1159	0.2189	0.057*
C12	0.5431 (4)	−0.00930 (16)	0.1890 (2)	0.0362 (7)
C13	0.7915 (4)	0.00404 (19)	0.3364 (3)	0.0481 (9)
H13	0.8215	−0.0438	0.3523	0.058*
C14	0.8710 (5)	0.0619 (2)	0.3822 (3)	0.0493 (9)
H14	0.9655	0.0622	0.4364	0.059*
C15	0.7838 (4)	0.12364 (18)	0.3324 (2)	0.0385 (7)
C31	0.1612 (7)	0.4606 (4)	0.1058 (4)	0.111 (2)
H31A	0.2316	0.4733	0.1694	0.166*
H31B	0.0442	0.4747	0.1012	0.166*
H31C	0.2027	0.4852	0.0563	0.166*
Cu1	0.44408 (4)	0.138051 (18)	0.15183 (3)	0.03011 (13)
N1	0.2516 (3)	0.13245 (13)	0.02083 (18)	0.0343 (6)
N2	0.4373 (3)	0.03481 (13)	0.12916 (18)	0.0334 (6)
N3	0.6532 (3)	0.10168 (13)	0.25914 (18)	0.0347 (6)
N4	0.6587 (3)	0.02680 (13)	0.26229 (19)	0.0370 (6)
N5	0.8209 (4)	0.19272 (15)	0.3524 (2)	0.0529 (8)
H5A	0.7596	0.2259	0.3174	0.063*
H5B	0.9063	0.2044	0.4004	0.063*
O1	0.4992 (3)	0.35921 (11)	0.0990 (2)	0.0515 (6)
O2	0.6055 (3)	0.25862 (13)	0.02490 (17)	0.0525 (6)
O3	0.4648 (3)	0.24075 (11)	0.15597 (17)	0.0434 (6)
O4	0.7439 (3)	0.29447 (14)	0.18900 (18)	0.0538 (7)
O5	0.2591 (3)	0.13987 (12)	0.24556 (18)	0.0480 (6)
H4	0.1973	0.1805	0.2347	0.072*
H5	0.3107	0.1423	0.3096	0.072*
O6	0.1687 (4)	0.3845 (2)	0.0919 (3)	0.0984 (12)
H12	0.2611	0.3620	0.0915	0.148*
O7	0.0713 (4)	0.2581 (2)	0.1844 (3)	0.1175 (16)
H6	0.1204	0.2972	0.1766	0.176*
H7	−0.0386	0.2670	0.1828	0.176*
O8	0.3587 (5)	0.1592 (2)	0.4472 (3)	0.1121 (14)
H17	0.4504	0.1598	0.4992	0.168*
H18	0.2726	0.1752	0.4720	0.168*
S1	0.58095 (10)	0.28883 (4)	0.11578 (6)	0.03254 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.046 (2)	0.046 (2)	0.0389 (18)	−0.0066 (15)	0.0051 (15)	0.0077 (15)
C2	0.046 (2)	0.077 (3)	0.0372 (19)	−0.0089 (19)	−0.0022 (16)	0.0165 (19)
C3	0.0403 (19)	0.086 (3)	0.0324 (18)	−0.0197 (19)	0.0020 (15)	−0.0022 (19)
C4	0.0389 (18)	0.061 (2)	0.0299 (16)	−0.0185 (16)	0.0142 (14)	−0.0122 (15)
C5	0.0363 (17)	0.0417 (17)	0.0304 (15)	−0.0119 (14)	0.0127 (13)	−0.0075 (13)
C6	0.0352 (16)	0.0366 (16)	0.0381 (17)	−0.0090 (13)	0.0175 (14)	−0.0069 (14)
C7	0.0465 (19)	0.0374 (17)	0.053 (2)	−0.0135 (15)	0.0298 (16)	−0.0170 (16)
C8	0.057 (2)	0.048 (2)	0.064 (3)	−0.0223 (18)	0.032 (2)	−0.0255 (19)
C9	0.050 (2)	0.070 (3)	0.044 (2)	−0.0303 (19)	0.0202 (17)	−0.0283 (19)
C10	0.061 (2)	0.0277 (16)	0.075 (3)	−0.0035 (16)	0.039 (2)	−0.0118 (18)
C11	0.053 (2)	0.0319 (17)	0.064 (2)	0.0059 (15)	0.0256 (18)	0.0052 (16)
C12	0.0389 (17)	0.0307 (15)	0.0439 (18)	0.0049 (13)	0.0199 (15)	0.0023 (14)
C13	0.053 (2)	0.048 (2)	0.043 (2)	0.0213 (17)	0.0115 (17)	0.0141 (17)
C14	0.049 (2)	0.055 (2)	0.0372 (18)	0.0147 (17)	−0.0026 (16)	0.0036 (16)
C15	0.0375 (17)	0.0467 (19)	0.0293 (16)	0.0077 (14)	0.0048 (14)	0.0000 (14)
C31	0.090 (4)	0.147 (6)	0.096 (4)	0.053 (4)	0.026 (3)	0.035 (4)
Cu1	0.0322 (2)	0.0259 (2)	0.0296 (2)	−0.00044 (14)	0.00279 (15)	−0.00061 (14)
N1	0.0318 (13)	0.0393 (14)	0.0302 (13)	−0.0064 (11)	0.0049 (11)	0.0000 (11)
N2	0.0378 (14)	0.0286 (13)	0.0354 (14)	−0.0010 (10)	0.0123 (12)	−0.0030 (11)
N3	0.0386 (15)	0.0293 (13)	0.0341 (14)	0.0055 (11)	0.0049 (11)	0.0012 (11)
N4	0.0407 (15)	0.0326 (14)	0.0376 (14)	0.0116 (11)	0.0095 (12)	0.0035 (11)
N5	0.0575 (19)	0.0450 (17)	0.0422 (17)	0.0028 (14)	−0.0134 (15)	−0.0033 (14)
O1	0.0539 (15)	0.0301 (12)	0.0713 (18)	0.0039 (10)	0.0170 (13)	0.0049 (11)
O2	0.0635 (16)	0.0543 (15)	0.0387 (13)	−0.0005 (12)	0.0110 (12)	−0.0137 (11)
O3	0.0458 (13)	0.0280 (11)	0.0564 (15)	−0.0053 (9)	0.0129 (11)	−0.0011 (10)
O4	0.0359 (13)	0.0714 (17)	0.0474 (15)	−0.0082 (12)	−0.0021 (11)	−0.0075 (12)
O5	0.0465 (14)	0.0536 (15)	0.0445 (14)	0.0042 (11)	0.0128 (11)	−0.0029 (11)
O6	0.054 (2)	0.094 (3)	0.153 (4)	0.0053 (18)	0.037 (2)	0.015 (2)
O7	0.077 (2)	0.103 (3)	0.195 (4)	0.046 (2)	0.075 (3)	0.068 (3)
O8	0.097 (3)	0.176 (4)	0.057 (2)	0.041 (3)	0.0068 (19)	−0.019 (2)
S1	0.0335 (4)	0.0271 (4)	0.0331 (4)	−0.0026 (3)	0.0009 (3)	−0.0041 (3)

Geometric parameters (Å, º) top

C1—N1	1.318 (4)	C14—C15	1.427 (4)
C1—C2	1.408 (5)	C14—H14	0.9300
C1—H1	0.9300	C15—N5	1.325 (4)
C2—C3	1.349 (6)	C15—N3	1.336 (4)
C2—H2	0.9300	C31—O6	1.424 (6)
C3—C4	1.404 (5)	C31—H31A	0.9600
C3—H3	0.9300	C31—H31B	0.9600
C4—C5	1.402 (4)	C31—H31C	0.9600
C4—C9	1.439 (5)	Cu1—O3	1.906 (2)
C5—N1	1.358 (4)	Cu1—N2	1.934 (2)
C5—C6	1.410 (4)	Cu1—N3	2.068 (2)
C6—N2	1.348 (4)	Cu1—N1	2.090 (2)
C6—C7	1.400 (4)	Cu1—O5	2.220 (2)
C7—C10	1.421 (5)	N3—N4	1.386 (3)
C7—C8	1.424 (5)	N5—H5A	0.8600
C8—C9	1.342 (5)	N5—H5B	0.8600
C8—H8	0.9300	O1—S1	1.450 (2)
C9—H9	0.9300	O2—S1	1.455 (2)
C10—C11	1.354 (5)	O3—S1	1.498 (2)
C10—H10	0.9300	O4—S1	1.451 (2)
C11—C12	1.411 (4)	O5—H4	0.8913
C11—H11	0.9300	O5—H5	0.8938
C12—N2	1.317 (4)	O6—H12	0.8515
C12—N4	1.375 (4)	O7—H6	0.8442
C13—C14	1.328 (5)	O7—H7	0.8906
C13—N4	1.357 (4)	O8—H17	0.8981
C13—H13	0.9300	O8—H18	0.8983

N1—C1—C2	121.9 (3)	O6—C31—H31A	109.5
N1—C1—H1	119.1	O6—C31—H31B	109.5
C2—C1—H1	119.1	H31A—C31—H31B	109.5
C3—C2—C1	120.0 (4)	O6—C31—H31C	109.5
C3—C2—H2	120.0	H31A—C31—H31C	109.5
C1—C2—H2	120.0	H31B—C31—H31C	109.5
C2—C3—C4	120.4 (3)	O3—Cu1—N2	170.82 (10)
C2—C3—H3	119.8	O3—Cu1—N3	104.67 (10)
C4—C3—H3	119.8	N2—Cu1—N3	77.52 (10)
C5—C4—C3	115.5 (3)	O3—Cu1—N1	96.64 (10)
C5—C4—C9	117.5 (3)	N2—Cu1—N1	79.71 (10)
C3—C4—C9	127.0 (3)	N3—Cu1—N1	155.91 (10)
N1—C5—C4	124.5 (3)	O3—Cu1—O5	91.88 (9)
N1—C5—C6	116.3 (3)	N2—Cu1—O5	96.76 (9)
C4—C5—C6	119.2 (3)	N3—Cu1—O5	96.34 (10)
N2—C6—C7	121.9 (3)	N1—Cu1—O5	94.02 (10)
N2—C6—C5	115.0 (3)	C1—N1—C5	117.6 (3)
C7—C6—C5	123.1 (3)	C1—N1—Cu1	131.1 (2)
C6—C7—C10	115.8 (3)	C5—N1—Cu1	111.23 (19)
C6—C7—C8	116.3 (3)	C12—N2—C6	121.1 (3)
C10—C7—C8	127.9 (3)	C12—N2—Cu1	121.2 (2)
C9—C8—C7	121.8 (3)	C6—N2—Cu1	117.7 (2)
C9—C8—H8	119.1	C15—N3—N4	105.4 (2)
C7—C8—H8	119.1	C15—N3—Cu1	143.2 (2)
C8—C9—C4	122.1 (3)	N4—N3—Cu1	111.22 (18)
C8—C9—H9	118.9	C13—N4—C12	132.7 (3)
C4—C9—H9	118.9	C13—N4—N3	110.3 (3)
C11—C10—C7	121.8 (3)	C12—N4—N3	116.8 (2)
C11—C10—H10	119.1	C15—N5—H5A	120.0
C7—C10—H10	119.1	C15—N5—H5B	120.0
C10—C11—C12	118.1 (3)	H5A—N5—H5B	120.0
C10—C11—H11	120.9	S1—O3—Cu1	129.60 (14)
C12—C11—H11	120.9	Cu1—O5—H4	109.7
N2—C12—N4	112.6 (3)	Cu1—O5—H5	113.0
N2—C12—C11	121.2 (3)	H4—O5—H5	103.1
N4—C12—C11	126.2 (3)	C31—O6—H12	123.5
C14—C13—N4	108.2 (3)	H6—O7—H7	109.3
C14—C13—H13	125.9	H17—O8—H18	103.3
N4—C13—H13	125.9	O1—S1—O4	109.94 (15)
C13—C14—C15	106.8 (3)	O1—S1—O2	110.92 (15)
C13—C14—H14	126.6	O4—S1—O2	110.86 (15)
C15—C14—H14	126.6	O1—S1—O3	107.19 (14)
N5—C15—N3	123.2 (3)	O4—S1—O3	107.99 (14)
N5—C15—C14	127.6 (3)	O2—S1—O3	109.84 (14)
N3—C15—C14	109.2 (3)

N1—C1—C2—C3	1.8 (6)	N4—C12—N2—C6	176.8 (3)
C1—C2—C3—C4	0.4 (6)	C11—C12—N2—C6	−2.9 (4)
C2—C3—C4—C5	−1.7 (5)	N4—C12—N2—Cu1	−3.3 (4)
C2—C3—C4—C9	179.0 (3)	C11—C12—N2—Cu1	177.0 (2)
C3—C4—C5—N1	0.9 (5)	C7—C6—N2—C12	0.9 (4)
C9—C4—C5—N1	−179.7 (3)	C5—C6—N2—C12	−177.8 (3)
C3—C4—C5—C6	−178.5 (3)	C7—C6—N2—Cu1	−179.0 (2)
C9—C4—C5—C6	0.9 (4)	C5—C6—N2—Cu1	2.3 (3)
N1—C5—C6—N2	−0.8 (4)	N3—Cu1—N2—C12	5.9 (2)
C4—C5—C6—N2	178.7 (3)	N1—Cu1—N2—C12	178.0 (2)
N1—C5—C6—C7	−179.5 (3)	O5—Cu1—N2—C12	−89.1 (2)
C4—C5—C6—C7	−0.1 (5)	N3—Cu1—N2—C6	−174.2 (2)
N2—C6—C7—C10	1.4 (4)	N1—Cu1—N2—C6	−2.1 (2)
C5—C6—C7—C10	−179.9 (3)	O5—Cu1—N2—C6	90.8 (2)
N2—C6—C7—C8	−179.2 (3)	N5—C15—N3—N4	179.5 (3)
C5—C6—C7—C8	−0.5 (5)	C14—C15—N3—N4	−0.4 (3)
C6—C7—C8—C9	0.3 (5)	N5—C15—N3—Cu1	−5.7 (6)
C10—C7—C8—C9	179.6 (3)	C14—C15—N3—Cu1	174.4 (3)
C7—C8—C9—C4	0.6 (5)	O3—Cu1—N3—C15	7.6 (4)
C5—C4—C9—C8	−1.2 (5)	N2—Cu1—N3—C15	178.4 (4)
C3—C4—C9—C8	178.2 (3)	N1—Cu1—N3—C15	159.1 (3)
C6—C7—C10—C11	−1.8 (5)	O5—Cu1—N3—C15	−86.0 (4)
C8—C7—C10—C11	178.9 (3)	O3—Cu1—N3—N4	−177.80 (18)
C7—C10—C11—C12	0.0 (5)	N2—Cu1—N3—N4	−6.98 (18)
C10—C11—C12—N2	2.5 (5)	N1—Cu1—N3—N4	−26.3 (4)
C10—C11—C12—N4	−177.3 (3)	O5—Cu1—N3—N4	88.58 (19)
N4—C13—C14—C15	−1.0 (4)	C14—C13—N4—C12	175.1 (3)
C13—C14—C15—N5	−179.0 (3)	C14—C13—N4—N3	0.8 (4)
C13—C14—C15—N3	0.8 (4)	N2—C12—N4—C13	−177.5 (3)
C2—C1—N1—C5	−2.6 (5)	C11—C12—N4—C13	2.2 (6)
C2—C1—N1—Cu1	179.4 (3)	N2—C12—N4—N3	−3.4 (4)
C4—C5—N1—C1	1.2 (5)	C11—C12—N4—N3	176.3 (3)
C6—C5—N1—C1	−179.3 (3)	C15—N3—N4—C13	−0.2 (3)
C4—C5—N1—Cu1	179.7 (2)	Cu1—N3—N4—C13	−176.9 (2)
C6—C5—N1—Cu1	−0.9 (3)	C15—N3—N4—C12	−175.6 (3)
O3—Cu1—N1—C1	−8.8 (3)	Cu1—N3—N4—C12	7.8 (3)
N2—Cu1—N1—C1	179.8 (3)	N3—Cu1—O3—S1	77.66 (19)
N3—Cu1—N1—C1	−161.0 (3)	N1—Cu1—O3—S1	−91.02 (19)
O5—Cu1—N1—C1	83.6 (3)	O5—Cu1—O3—S1	174.72 (18)
O3—Cu1—N1—C5	173.1 (2)	Cu1—O3—S1—O1	155.30 (18)
N2—Cu1—N1—C5	1.6 (2)	Cu1—O3—S1—O4	−86.3 (2)
N3—Cu1—N1—C5	20.8 (4)	Cu1—O3—S1—O2	34.7 (2)
O5—Cu1—N1—C5	−94.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H4···O7	0.89	1.79	2.671 (4)	167
O5—H5···O8	0.89	1.90	2.774 (4)	164
O6—H12···O1	0.85	1.89	2.668 (4)	152
O7—H6···O6	0.84	2.10	2.878 (5)	153
O7—H7···O4ⁱ	0.89	1.84	2.726 (4)	173
O8—H17···O6ⁱⁱ	0.90	2.07	2.906 (5)	154
O8—H18···O2ⁱⁱⁱ	0.90	2.09	2.957 (4)	163
N5—H5A···O4	0.86	2.19	2.916 (4)	143
N5—H5B···O2ⁱⁱ	0.86	2.17	3.022 (4)	175

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

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₁₅H₁₁N₅)(H₂O)]·CH₄O·2H₂O
M_r	506.98
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.0190 (13), 18.489 (3), 14.086 (2)
β (°)	104.551 (2)
V (Å³)	2021.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.22 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.772, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	11702, 4394, 3434
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.119, 1.03
No. of reflections	4394
No. of parameters	281
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.31

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O3	1.906 (2)	Cu1—N1	2.090 (2)
Cu1—N2	1.934 (2)	Cu1—O5	2.220 (2)
Cu1—N3	2.068 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H4···O7	0.89	1.79	2.671 (4)	167.0
O5—H5···O8	0.89	1.90	2.774 (4)	163.5
O6—H12···O1	0.85	1.89	2.668 (4)	152.0
O7—H6···O6	0.84	2.10	2.878 (5)	153.1
O7—H7···O4ⁱ	0.89	1.84	2.726 (4)	173.2
O8—H17···O6ⁱⁱ	0.90	2.07	2.906 (5)	153.9
O8—H18···O2ⁱⁱⁱ	0.90	2.09	2.957 (4)	163.2
N5—H5A···O4	0.86	2.19	2.916 (4)	142.5
N5—H5B···O2ⁱⁱ	0.86	2.17	3.022 (4)	174.5

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

Acknowledgements

The authors thank the Natural Science Foundation of Shandong Province of China (No. ZR2009BM026).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2000). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, H., Zhang, S. D., Xie, L. M., Yu, L. & Shi, J. M. (2011a). J. Coord. Chem. 64, 1456–1468. Web of Science CSD CrossRef CAS Google Scholar
Li, H., Zhang, S. D., Xie, L. M., Yu, L. & Shi, J. M. (2011b). J. Coord. Chem. 64, 3595–3608. Web of Science CSD CrossRef CAS Google Scholar
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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