catena-Poly[[[tetra­kis­(4-methyl­pyridine-κN)copper(II)]-μ-sulfato-κ2O:O′] 4.393-hydrate]

Alam, N.; Shahid, M.; Mazhar, M.; Al-Jassabi, S.; Zeller, M.; Hunter, A.D.

doi:10.1107/S1600536811006325

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Pages m375-m376

doi:10.1107/S1600536811006325

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catena-Poly[[[tetrakis(4-methylpyridine-κN)copper(II)]-μ-sulfato-κ²O:O′] 4.393-hydrate]

Naveed Alam,^a Muhammad Shahid,^a ^* Muhammad Mazhar,^b Saad Al-Jassabi,^c Matthias Zeller ^d and Allen D. Hunter ^d

^aDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan, ^bDepartment of Chemistry, Faculty of Science, University of Malaya, Lembah Pantai, 50603 Kuala Lumpur, Malaysia, ^cDepartment of Biochemistry, Faculty of Science, University of Malaya, Lembah Pantai, 50603 Kuala Lumpur, Malaysia, and ^dSTaRBURSTT-Cyberdiffraction Consortium at YSU and Department of Chemistry, Youngstown State University, 1 University Plaza, Youngstown, Ohio 44555, USA
^*Correspondence e-mail: shahid_chme@yahoo.com

(Received 10 February 2011; accepted 19 February 2011; online 26 February 2011)

The structure of the title compound, {[Cu(SO₄)(C₆H₇N)₄]·4.393H₂O}_n, consists of Cu²⁺ ions surrounded in a square-planar fashion by 4-methylpyridine ligands, forming two crystallographically independent Cu{H₃C(C₅H₄N)}₄ units that are both located on crystallographic inversion centers. The Cu(4-methylpyridine)₄ units are, in turn, connected with each other via bridging sulfate anions, leading to the formation of infinite [Cu{H₃C(C₅H₄N)}₄SO₄]_n zigzag chains along [001]. The completed coordination spheres of the Cu²⁺ ions are slightly distorted octahedral. The axial Cu—O bonds are elongated [average length = 2.42 (4) Å] compared to the equatorial Cu—N bonds [average length = 2.043 (2) Å]. The interstitial space between the chains is filled with uncoordinated water molecules that consolidate the structure through O—H⋯O hydrogen bonding. One of the five crystallographically independent solvent water molecules is partially occupied with an occupancy factor of 0.396 (4). Due to hydrogen bonding between symmetry-equivalent water molecules across inversion centers, several of the water H atoms are disordered in 1:1 ratios over mutually exclusive positions. The crystal under investigation was found to be non-merohedrally twinned in a 0.789 (1):0.211 (1) ratio by a 180° rotation around the reciprocal b axis.

Related literature

For the structures of related binuclear copper(II) complexes, see: Shahid et al. (2008 , 2009 ).

Experimental

Crystal data

[Cu(SO₄)(C₆H₇N)₄]·4.393H₂O
M_r = 611.27
Triclinic, $[P \overline 1]$
a = 10.4688 (12) Å
b = 11.6327 (14) Å
c = 12.8300 (15) Å
α = 78.672 (3)°
β = 87.609 (3)°
γ = 67.571 (3)°
V = 1415.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 100 K
0.60 × 0.45 × 0.40 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (TWINABS; Bruker, 2008 ) T_min = 0.607, T_max = 0.746
16814 measured reflections
6963 independent reflections
6170 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.118
S = 1.06
6963 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6ⁱ	0.85	2.04	2.887 (4)	173
O5—H5B⋯O4ⁱⁱ	0.85	2.01	2.843 (4)	168
O6—H6A⋯O6ⁱ	0.84	2.34	2.983 (6)	133
O6—H6B⋯O4ⁱⁱ	0.85	1.92	2.762 (4)	172
O6—H6C⋯O8	0.85	1.98	2.804 (5)	163
O7—H7A⋯O5	0.84	2.16	2.906 (4)	148
O7—H7B⋯O3ⁱⁱⁱ	0.85	2.13	2.923 (4)	157
O8—H8A⋯O3ⁱⁱ	0.84	2.42	2.788 (4)	107
O8—H8B⋯O6	0.85	2.04	2.804 (5)	149
O8—H8C⋯O8^iv	0.85	1.87	2.710 (7)	176
O9—H9A⋯O6	0.84	2.48	3.210 (7)	145
O9—H9B⋯O3ⁱⁱ	0.84	2.22	3.063 (7)	175
O9—H9B⋯O4ⁱⁱ	0.84	2.71	3.275 (7)	126
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y-1, z; (iii) x+1, y-1, z; (iv) -x, -y+1, -z.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2009 ); data reduction: CELL NOW (Bruker, 2009) and SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006325/wm2458sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006325/wm2458Isup2.hkl

checkCIF report

Comment top

In relation to our previous work on the structural chemistry of copper complexes (Shahid et al., 2008; 2009) the title compound was prepared as the unintended product of the reaction of CuSO₄^.5H₂O with pyrolidine in acetone and 4-methylpyridine.

In the title structure (Fig. 1), two crystallographically independent Cu²⁺ ions are each located on an inversion center. Their coordination environments are distorted octahedral, with a CuN₄O₂ set of ligating atoms, composed of four N atoms from four 4-methylpyridine groups and two O atoms of two sulfate anions. The equatorial plane is made up of four N atoms of the 4-methylpyridine ligands, N1, N1ⁱ, N2 and N2ⁱ for Cu1 and N3, N3ⁱⁱ, N4 and N4ⁱⁱ for Cu2 (symmetry operators (i) -x + 1, -y + 2, -z + 1; (ii) -x + 1, -y + 2, -z.), with distances ranging between 2.041 (2) and 2.046 (2) Å. The O atoms O1, O1ⁱ, O2 and O2ⁱⁱ of the sulfate anion are bonded at the axial positions of Cu1 and Cu2, respectively, resulting in considerably longer Cu—O bonds of 2.393 (2) Å for Cu1—O1 and 2.443 (2) Å for Cu2—O2.

The bridging sulfate ions connect the Cu(4-methylpyridine)₄ units to form infinite [Cu{H₃C(C₅H₄N)}₄SO₄]_n zigzag chains along the [001] direction of the crystal (Fig. 2). The shape of the zigzag chain follows the coordination geometry of the copper and sulfate ions: Cu—O—S angles are close to 180° (169.62 (13) for S1—O1—Cu1 and 172.99 (1) for S1—O2—Cu2), the O—Cu—O angles are exactly 180° (due to the location of the copper ions on inversion centers). The angles of the zigzag chain, represented by the Cu—S—Cu angles, thus follow closely the tetrahedral sulfate O—S—O angles and are 111.73 ° (the O—S—O angles range between 108.76 (12) and 110.04 (13)°).

Parallel zigzag chains interdigitate as shown in Fig. 3, but interstitial space is left between neighboring molecules. Along the a-axis neighboring sulfate ions are connected through O—H···O hydrogen bonds mediated by the water molecules O5 and O7 to form infinite {O···H₂O···H₂O···O···H₂O···H₂O···}_n chains. Parallel pairs of these chains are connected with each other through additional O—H···O hydrogen bonds mediated by the water molecules of O6 and O8. Due to hydrogen bonding between symmetry equivalent water molecules across inversion centers, the H atoms of O6 and O8 are partially disordered over mutually exclusive positions (see refinement section for details). The connection of the sulfate ions with these water molecules creates flat strands made up of slightly wobbly single molecule layers of tightly hydrogen-bonded water and sulfate molecules about seven to eight Å wide that stretch infinitely parallel to the a-axis (Figs. 3 and 4). The last of the five crystallographically independent water solvate molecules (O9) is not part of these strands but is located about three Å away and is only weakly hydrogen bonded with the other water molecules (Fig. 4). It is only partially occupied with a refined occupancy factor of 0.396 (4). For details and numerical values of the hydrogen bonding geometries, including symmetry operators, see: Table 1.

Related literature top

For the structures of related binuclear copper(II) complexes, see: Shahid et al. (2008, 2009). Scheme should show 4.393H₂O

Experimental top

CuSO₄^.5H₂O (0.30 g, 1.21 mmol) was added directly to a stirred solution of pyrolidine (0.5 g, 2.43 mmole) in 20 ml acetone. The contents were stirred until complete dissolution of the salt to which about 30 ml of 4-methylpyridine was added and stirring was continued for another hour. Insoluble matter was removed by filtration and slow evaporation of the reaction mixture at room temperature gave the title compound as blue crystals after three weeks. Yield 60% (0.44 g), m.p. 373 K. Elemental analysis: calculated (found): C 47.15(47.66), H 6.06(5.92), N 9.20(8.95)%.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2009); data reduction: CELL NOW (Bruker, 2009) and SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level with atom labeling. Symmetry transformations used to generate equivalent atoms: (i) -x + 1,-y + 2,-z + 1; (ii) -x + 1,-y + 2,-z. For the water molecules all disordered H atoms are shown.
	Fig. 2. View of the polymeric zigzag chains along the [001] direction. Symmetry transformations used to generate equivalent atoms: (i) -x + 1, -y + 2,-z + 1; (ii) -x + 1,-y + 2,-z.
	Fig. 3. Interdigitation between parallel zigzag chains and hydrogen bonding. View is down the c axis along the direction of the polymeric chains shown in Fig. 2. Note the interdigitation of tolyl groups of parallel chains along the a axis and the water filled areas between chains along the b axis. Hydrogen bonds are indicated by dashed light blue lines. Bands of H–bonded water molecules stretch infinitely parallel to the a axis.
	Fig. 4. Packing and hydrogen bonding in the structure of the title compound. View is down the a axis. Hydrogen bonds are indicated by dashed light blue lines (H atoms omitted for clarity). Layers of H bonded water molecules stretch infinitely parallel to the a-axis. The single water molecule O9 that is not part of the water cluster is clearly visible in this view.

catena-Poly[[[tetrakis(4-methylpyridine-κN)copper(II)]- µ-sulfato-κ²O:O'] 4.392-hydrate] top

Crystal data top

[Cu(SO₄)(C₆H₇N)₄]·4.393H₂O	Z = 2
M_r = 611.27	F(000) = 642
Triclinic, P1	D_x = 1.434 Mg m⁻³
Hall symbol: -P 1	Melting point: 373 K
a = 10.4688 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6327 (14) Å	Cell parameters from 4676 reflections
c = 12.8300 (15) Å	θ = 2.3–30.4°
α = 78.672 (3)°	µ = 0.90 mm⁻¹
β = 87.609 (3)°	T = 100 K
γ = 67.571 (3)°	Block, blue
V = 1415.2 (3) Å³	0.60 × 0.45 × 0.40 mm

Data collection top

Bruker SMART APEX CCD diffractometer	6963 independent reflections
Radiation source: fine-focus sealed tube	6170 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 28.3°, θ_min = 1.6°
Absorption correction: multi-scan (TWINABS; Bruker, 2008)	h = −13→13
T_min = 0.607, T_max = 0.746	k = −15→15
16814 measured reflections	l = 0→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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0573P)² + 1.4896P] where P = (F_o² + 2F_c²)/3
6963 reflections	(Δ/σ)_max < 0.001
361 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.61 e Å⁻³

Crystal data top

[Cu(SO₄)(C₆H₇N)₄]·4.393H₂O	γ = 67.571 (3)°
M_r = 611.27	V = 1415.2 (3) Å³
Triclinic, P1	Z = 2
a = 10.4688 (12) Å	Mo Kα radiation
b = 11.6327 (14) Å	µ = 0.90 mm⁻¹
c = 12.8300 (15) Å	T = 100 K
α = 78.672 (3)°	0.60 × 0.45 × 0.40 mm
β = 87.609 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	6963 independent reflections
Absorption correction: multi-scan (TWINABS; Bruker, 2008)	6170 reflections with I > 2σ(I)
T_min = 0.607, T_max = 0.746	R_int = 0.033
16814 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.06	Δρ_max = 0.68 e Å⁻³
6963 reflections	Δρ_min = −0.61 e Å⁻³
361 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	Occ. (<1)
C1	0.7599 (3)	1.0000 (3)	0.5809 (2)	0.0204 (5)
H1	0.7594	0.9263	0.6281	0.024*
C2	0.8641 (3)	1.0426 (3)	0.5935 (2)	0.0231 (5)
H2	0.9329	0.9984	0.6488	0.028*
C3	0.8680 (3)	1.1497 (3)	0.5255 (2)	0.0230 (5)
C4	0.7680 (3)	1.2070 (3)	0.4436 (2)	0.0254 (6)
H4	0.7692	1.2784	0.3932	0.030*
C5	0.6665 (3)	1.1597 (3)	0.4355 (2)	0.0242 (6)
H5	0.5990	1.1999	0.3789	0.029*
C6	0.9755 (3)	1.2030 (3)	0.5399 (3)	0.0313 (6)
H6F	0.9338	1.2775	0.5729	0.047*
H6E	1.0100	1.2278	0.4704	0.047*
H6D	1.0523	1.1385	0.5856	0.047*
C7	0.6771 (3)	0.7248 (3)	0.5052 (2)	0.0259 (6)
H7	0.6453	0.7125	0.5754	0.031*
C8	0.7656 (4)	0.6209 (3)	0.4678 (2)	0.0318 (7)
H8	0.7943	0.5392	0.5123	0.038*
C9	0.8136 (3)	0.6346 (3)	0.3647 (2)	0.0272 (6)
C10	0.9073 (4)	0.5230 (3)	0.3195 (3)	0.0451 (9)
H10A	0.8548	0.4736	0.3050	0.068*
H10B	0.9834	0.4695	0.3709	0.068*
H10C	0.9449	0.5532	0.2533	0.068*
C11	0.7700 (3)	0.7568 (3)	0.3053 (2)	0.0224 (5)
H11	0.8015	0.7715	0.2353	0.027*
C12	0.6808 (3)	0.8575 (3)	0.3476 (2)	0.0212 (5)
H12	0.6517	0.9402	0.3048	0.025*
C13	0.4334 (3)	0.8651 (3)	0.2020 (2)	0.0216 (5)
H13	0.3870	0.9490	0.2138	0.026*
C14	0.4296 (3)	0.7646 (3)	0.2792 (2)	0.0208 (5)
H14	0.3811	0.7806	0.3424	0.025*
C15	0.4963 (3)	0.6413 (3)	0.2645 (2)	0.0253 (6)
C16	0.5674 (4)	0.6247 (3)	0.1714 (2)	0.0341 (7)
H16	0.6166	0.5416	0.1585	0.041*
C17	0.5667 (3)	0.7287 (3)	0.0975 (2)	0.0310 (6)
H17	0.6156	0.7150	0.0342	0.037*
C18	0.4934 (4)	0.5303 (3)	0.3466 (2)	0.0371 (8)
H18A	0.5735	0.5000	0.3960	0.056*
H18B	0.4967	0.4620	0.3112	0.056*
H18C	0.4082	0.5569	0.3860	0.056*
C19	0.7394 (3)	1.0233 (3)	0.0928 (2)	0.0228 (5)
H19	0.6692	1.0967	0.1105	0.027*
C20	0.8748 (3)	0.9916 (3)	0.1272 (2)	0.0258 (6)
H20	0.8958	1.0428	0.1676	0.031*
C21	0.9792 (3)	0.8852 (3)	0.1023 (2)	0.0256 (6)
C22	0.9428 (3)	0.8158 (3)	0.0406 (2)	0.0291 (6)
H22	1.0113	0.7430	0.0207	0.035*
C23	0.8054 (3)	0.8539 (3)	0.0084 (2)	0.0272 (6)
H23	0.7822	0.8067	−0.0349	0.033*
C24	1.1264 (3)	0.8448 (3)	0.1420 (2)	0.0328 (7)
H24A	1.1478	0.9201	0.1405	0.049*
H24B	1.1893	0.7918	0.0962	0.049*
H24C	1.1378	0.7964	0.2150	0.049*
Cu1	0.5000	1.0000	0.5000	0.01857 (11)
Cu2	0.5000	1.0000	0.0000	0.02031 (11)
N1	0.6596 (2)	1.0589 (2)	0.50462 (17)	0.0197 (4)
N2	0.6332 (2)	0.8438 (2)	0.44667 (17)	0.0196 (4)
N3	0.5002 (2)	0.8479 (2)	0.11114 (17)	0.0204 (4)
N4	0.7039 (2)	0.9544 (2)	0.03565 (17)	0.0208 (4)
O1	0.4432 (2)	1.11465 (19)	0.32076 (14)	0.0241 (4)
O2	0.4297 (2)	1.1372 (2)	0.13099 (15)	0.0257 (4)
O3	0.2438 (2)	1.2743 (2)	0.21897 (18)	0.0387 (6)
O4	0.4641 (3)	1.2969 (2)	0.20710 (19)	0.0389 (6)
O5	0.7247 (3)	0.3043 (2)	0.1438 (2)	0.0501 (7)
H5A	0.7007	0.3519	0.0826	0.075*
H5B	0.6529	0.2956	0.1714	0.075*
O6	0.3674 (3)	0.5172 (3)	0.0548 (2)	0.0568 (7)
H6A	0.4103	0.5011	−0.0008	0.085*	0.50
H6B	0.4034	0.4467	0.0972	0.085*
H6C	0.2905	0.5147	0.0399	0.085*	0.50
O7	0.9960 (3)	0.2146 (3)	0.2479 (2)	0.0567 (8)
H7A	0.9293	0.2632	0.2054	0.085*
H7B	1.0552	0.2449	0.2228	0.085*
O8	0.1306 (4)	0.4630 (4)	0.0397 (4)	0.0971 (15)
H8A	0.1109	0.4722	0.1027	0.146*
H8B	0.1842	0.5027	0.0261	0.146*	0.50
H8C	0.0507	0.4844	0.0125	0.146*	0.50
O9	0.2000 (7)	0.5327 (6)	0.2704 (5)	0.045 (2)	0.393 (8)
H9A	0.2311	0.5640	0.2151	0.067*	0.393 (8)
H9B	0.2166	0.4593	0.2590	0.067*	0.393 (8)
S3	0.39467 (7)	1.20521 (6)	0.21937 (5)	0.01904 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0229 (13)	0.0205 (12)	0.0186 (12)	−0.0087 (11)	−0.0004 (9)	−0.0046 (10)
C2	0.0201 (12)	0.0294 (14)	0.0220 (13)	−0.0095 (11)	−0.0012 (10)	−0.0099 (11)
C3	0.0187 (12)	0.0275 (14)	0.0274 (14)	−0.0106 (11)	0.0047 (10)	−0.0131 (11)
C4	0.0276 (14)	0.0269 (14)	0.0247 (14)	−0.0145 (12)	0.0019 (11)	−0.0035 (11)
C5	0.0278 (14)	0.0285 (14)	0.0198 (13)	−0.0162 (12)	−0.0028 (10)	−0.0002 (10)
C6	0.0259 (14)	0.0341 (16)	0.0411 (17)	−0.0166 (13)	0.0008 (12)	−0.0126 (13)
C7	0.0371 (16)	0.0245 (14)	0.0176 (12)	−0.0145 (12)	−0.0017 (11)	−0.0015 (10)
C8	0.0478 (19)	0.0231 (14)	0.0235 (14)	−0.0138 (14)	−0.0010 (13)	−0.0013 (11)
C9	0.0316 (15)	0.0267 (15)	0.0241 (14)	−0.0111 (12)	−0.0026 (11)	−0.0056 (11)
C10	0.062 (2)	0.0287 (17)	0.0363 (19)	−0.0067 (17)	0.0047 (17)	−0.0091 (14)
C11	0.0238 (13)	0.0278 (14)	0.0184 (12)	−0.0128 (11)	0.0005 (10)	−0.0046 (10)
C12	0.0202 (12)	0.0258 (13)	0.0190 (12)	−0.0118 (11)	−0.0009 (10)	−0.0014 (10)
C13	0.0212 (13)	0.0235 (13)	0.0222 (13)	−0.0106 (11)	−0.0007 (10)	−0.0044 (10)
C14	0.0221 (12)	0.0275 (14)	0.0178 (12)	−0.0145 (11)	0.0002 (10)	−0.0051 (10)
C15	0.0333 (15)	0.0262 (14)	0.0187 (13)	−0.0148 (12)	−0.0032 (11)	−0.0017 (10)
C16	0.053 (2)	0.0220 (14)	0.0234 (14)	−0.0103 (14)	0.0054 (13)	−0.0057 (11)
C17	0.0429 (18)	0.0297 (15)	0.0183 (13)	−0.0117 (14)	0.0062 (12)	−0.0053 (11)
C18	0.062 (2)	0.0293 (16)	0.0227 (15)	−0.0231 (16)	0.0065 (14)	−0.0013 (12)
C19	0.0259 (13)	0.0262 (14)	0.0201 (12)	−0.0157 (11)	−0.0012 (10)	−0.0010 (10)
C20	0.0290 (14)	0.0341 (15)	0.0208 (13)	−0.0211 (13)	−0.0035 (10)	−0.0006 (11)
C21	0.0212 (13)	0.0377 (16)	0.0175 (12)	−0.0147 (12)	−0.0016 (10)	0.0032 (11)
C22	0.0232 (14)	0.0358 (16)	0.0252 (14)	−0.0078 (12)	−0.0004 (11)	−0.0059 (12)
C23	0.0280 (14)	0.0338 (15)	0.0223 (13)	−0.0134 (13)	−0.0044 (11)	−0.0065 (12)
C24	0.0235 (14)	0.0469 (18)	0.0278 (15)	−0.0162 (14)	−0.0024 (11)	−0.0009 (13)
Cu1	0.0212 (2)	0.0220 (2)	0.0169 (2)	−0.01266 (19)	−0.00015 (16)	−0.00454 (18)
Cu2	0.0198 (2)	0.0240 (2)	0.0176 (2)	−0.0110 (2)	−0.00355 (16)	0.00135 (18)
N1	0.0229 (11)	0.0248 (11)	0.0158 (10)	−0.0127 (9)	0.0005 (8)	−0.0060 (8)
N2	0.0237 (11)	0.0233 (11)	0.0163 (10)	−0.0141 (9)	−0.0028 (8)	−0.0025 (8)
N3	0.0213 (11)	0.0236 (11)	0.0178 (10)	−0.0103 (9)	−0.0041 (8)	−0.0027 (9)
N4	0.0221 (11)	0.0242 (11)	0.0172 (10)	−0.0119 (9)	−0.0015 (8)	0.0003 (8)
O1	0.0311 (10)	0.0295 (10)	0.0130 (8)	−0.0145 (9)	−0.0030 (7)	−0.0002 (7)
O2	0.0331 (11)	0.0319 (11)	0.0149 (9)	−0.0143 (9)	0.0015 (8)	−0.0069 (8)
O3	0.0250 (11)	0.0461 (14)	0.0315 (12)	−0.0004 (10)	0.0011 (9)	−0.0046 (10)
O4	0.0571 (15)	0.0289 (11)	0.0373 (13)	−0.0282 (11)	−0.0223 (11)	0.0077 (9)
O5	0.0516 (16)	0.0386 (14)	0.0540 (16)	−0.0131 (12)	−0.0121 (13)	−0.0011 (12)
O6	0.077 (2)	0.0500 (17)	0.0409 (15)	−0.0260 (16)	−0.0023 (14)	0.0007 (13)
O7	0.0577 (17)	0.0562 (17)	0.0492 (16)	−0.0260 (15)	−0.0123 (13)	0.0174 (14)
O8	0.066 (2)	0.089 (3)	0.123 (3)	−0.044 (2)	−0.044 (2)	0.050 (2)
O9	0.049 (4)	0.044 (4)	0.045 (4)	−0.017 (3)	0.001 (3)	−0.017 (3)
S3	0.0231 (3)	0.0207 (3)	0.0147 (3)	−0.0099 (2)	−0.0032 (2)	−0.0026 (2)

Geometric parameters (Å, º) top

C1—N1	1.343 (3)	C19—N4	1.342 (3)
C1—C2	1.386 (4)	C19—C20	1.388 (4)
C1—H1	0.9500	C19—H19	0.9500
C2—C3	1.387 (4)	C20—C21	1.386 (4)
C2—H2	0.9500	C20—H20	0.9500
C3—C4	1.389 (4)	C21—C22	1.391 (4)
C3—C6	1.509 (4)	C21—C24	1.508 (4)
C4—C5	1.386 (4)	C22—C23	1.388 (4)
C4—H4	0.9500	C22—H22	0.9500
C5—N1	1.348 (4)	C23—N4	1.341 (4)
C5—H5	0.9500	C23—H23	0.9500
C6—H6F	0.9800	C24—H24A	0.9800
C6—H6E	0.9800	C24—H24B	0.9800
C6—H6D	0.9800	C24—H24C	0.9800
C7—N2	1.352 (4)	Cu1—N1ⁱ	2.041 (2)
C7—C8	1.373 (4)	Cu1—N1	2.041 (2)
C7—H7	0.9500	Cu1—N2	2.046 (2)
C8—C9	1.397 (4)	Cu1—N2ⁱ	2.046 (2)
C8—H8	0.9500	Cu1—O1	2.3926 (18)
C9—C11	1.385 (4)	Cu1—O1ⁱ	2.3926 (18)
C9—C10	1.503 (4)	Cu2—N4ⁱⁱ	2.042 (2)
C10—H10A	0.9800	Cu2—N4	2.042 (2)
C10—H10B	0.9800	Cu2—N3	2.042 (2)
C10—H10C	0.9800	Cu2—N3ⁱⁱ	2.042 (2)
C11—C12	1.382 (4)	Cu2—O2ⁱⁱ	2.443 (2)
C11—H11	0.9500	Cu2—O2	2.443 (2)
C12—N2	1.348 (3)	O1—S3	1.4726 (19)
C12—H12	0.9500	O2—S3	1.464 (2)
C13—N3	1.344 (3)	O3—S3	1.473 (2)
C13—C14	1.387 (4)	O4—S3	1.485 (2)
C13—H13	0.9500	O5—H5A	0.8515
C14—C15	1.382 (4)	O5—H5B	0.8498
C14—H14	0.9500	O6—H6A	0.8408
C15—C16	1.388 (4)	O6—H6B	0.8470
C15—C18	1.507 (4)	O6—H6C	0.8472
C16—C17	1.381 (4)	O7—H7A	0.8445
C16—H16	0.9500	O7—H7B	0.8477
C17—N3	1.336 (4)	O8—H8A	0.8431
C17—H17	0.9500	O8—H8B	0.8459
C18—H18A	0.9800	O8—H8C	0.8456
C18—H18B	0.9800	O9—H9A	0.8436
C18—H18C	0.9800	O9—H9B	0.8448

N1—C1—C2	122.6 (3)	C22—C21—C24	121.1 (3)
N1—C1—H1	118.7	C23—C22—C21	119.3 (3)
C2—C1—H1	118.7	C23—C22—H22	120.3
C1—C2—C3	120.0 (3)	C21—C22—H22	120.3
C1—C2—H2	120.0	N4—C23—C22	123.0 (3)
C3—C2—H2	120.0	N4—C23—H23	118.5
C2—C3—C4	117.3 (2)	C22—C23—H23	118.5
C2—C3—C6	121.7 (3)	C21—C24—H24A	109.5
C4—C3—C6	121.0 (3)	C21—C24—H24B	109.5
C5—C4—C3	119.7 (3)	H24A—C24—H24B	109.5
C5—C4—H4	120.1	C21—C24—H24C	109.5
C3—C4—H4	120.1	H24A—C24—H24C	109.5
N1—C5—C4	122.7 (3)	H24B—C24—H24C	109.5
N1—C5—H5	118.7	N1ⁱ—Cu1—N1	180.00 (11)
C4—C5—H5	118.7	N1ⁱ—Cu1—N2	91.28 (9)
C3—C6—H6F	109.5	N1—Cu1—N2	88.72 (9)
C3—C6—H6E	109.5	N1ⁱ—Cu1—N2ⁱ	88.72 (9)
H6F—C6—H6E	109.5	N1—Cu1—N2ⁱ	91.28 (9)
C3—C6—H6D	109.5	N2—Cu1—N2ⁱ	179.999 (1)
H6F—C6—H6D	109.5	N1ⁱ—Cu1—O1	90.27 (8)
H6E—C6—H6D	109.5	N1—Cu1—O1	89.73 (8)
N2—C7—C8	122.9 (3)	N2—Cu1—O1	90.38 (8)
N2—C7—H7	118.5	N2ⁱ—Cu1—O1	89.62 (8)
C8—C7—H7	118.5	N1ⁱ—Cu1—O1ⁱ	89.73 (8)
C7—C8—C9	120.4 (3)	N1—Cu1—O1ⁱ	90.27 (8)
C7—C8—H8	119.8	N2—Cu1—O1ⁱ	89.62 (8)
C9—C8—H8	119.8	N2ⁱ—Cu1—O1ⁱ	90.38 (8)
C11—C9—C8	116.6 (3)	O1—Cu1—O1ⁱ	180.0
C11—C9—C10	121.3 (3)	N4ⁱⁱ—Cu2—N4	180.0
C8—C9—C10	122.1 (3)	N4ⁱⁱ—Cu2—N3	89.63 (9)
C9—C10—H10A	109.5	N4—Cu2—N3	90.37 (9)
C9—C10—H10B	109.5	N4ⁱⁱ—Cu2—N3ⁱⁱ	90.37 (9)
H10A—C10—H10B	109.5	N4—Cu2—N3ⁱⁱ	89.63 (9)
C9—C10—H10C	109.5	N3—Cu2—N3ⁱⁱ	179.999 (1)
H10A—C10—H10C	109.5	N4—Cu2—O2ⁱⁱ	88.90 (8)
H10B—C10—H10C	109.5	N4ⁱⁱ—Cu2—O2ⁱⁱ	91.11 (8)
C12—C11—C9	120.2 (3)	N3—Cu2—O2ⁱⁱ	88.72 (8)
C12—C11—H11	119.9	N3ⁱⁱ—Cu2—O2ⁱⁱ	91.28 (8)
C9—C11—H11	119.9	N4—Cu2—O2	91.11 (8)
N2—C12—C11	123.1 (3)	N4ⁱⁱ—Cu2—O2	88.90 (8)
N2—C12—H12	118.5	N3—Cu2—O2	91.28 (8)
C11—C12—H12	118.5	N3ⁱⁱ—Cu2—O2	88.72 (8)
N3—C13—C14	122.4 (3)	O2ⁱⁱ—Cu2—O2	180.000 (1)
N3—C13—H13	118.8	C1—N1—C5	117.5 (2)
C14—C13—H13	118.8	C1—N1—Cu1	120.11 (18)
C15—C14—C13	120.2 (3)	C5—N1—Cu1	122.30 (18)
C15—C14—H14	119.9	C12—N2—C7	116.8 (2)
C13—C14—H14	119.9	C12—N2—Cu1	119.50 (19)
C14—C15—C16	116.9 (3)	C7—N2—Cu1	123.72 (19)
C14—C15—C18	121.5 (3)	C17—N3—C13	117.5 (2)
C16—C15—C18	121.7 (3)	C17—N3—Cu2	122.05 (19)
C17—C16—C15	120.1 (3)	C13—N3—Cu2	120.41 (19)
C17—C16—H16	120.0	C23—N4—C19	117.7 (2)
C15—C16—H16	120.0	C23—N4—Cu2	122.75 (19)
N3—C17—C16	122.9 (3)	C19—N4—Cu2	119.52 (19)
N3—C17—H17	118.5	S3—O1—Cu1	169.60 (13)
C16—C17—H17	118.5	H5A—O5—H5B	107.6
C15—C18—H18A	109.5	H6A—O6—H6B	101.2
C15—C18—H18B	109.5	H6A—O6—H6C	101.0
H18A—C18—H18B	109.5	H6B—O6—H6C	100.4
C15—C18—H18C	109.5	H7A—O7—H7B	97.7
H18A—C18—H18C	109.5	H8A—O8—H8B	100.6
H18B—C18—H18C	109.5	H8A—O8—H8C	100.5
N4—C19—C20	122.5 (3)	H8B—O8—H8C	126.9
N4—C19—H19	118.7	H9A—O9—H9B	100.6
C20—C19—H19	118.7	O2—S3—O1	109.72 (12)
C21—C20—C19	119.9 (3)	O2—S3—O3	109.57 (13)
C21—C20—H20	120.0	O1—S3—O3	110.06 (13)
C19—C20—H20	120.0	O2—S3—O4	109.34 (14)
C20—C21—C22	117.5 (3)	O1—S3—O4	108.76 (12)
C20—C21—C24	121.4 (3)	O3—S3—O4	109.37 (15)

N1—C1—C2—C3	−0.3 (4)	C11—C12—N2—C7	0.1 (4)
C1—C2—C3—C4	−2.6 (4)	C11—C12—N2—Cu1	−179.4 (2)
C1—C2—C3—C6	176.9 (3)	C8—C7—N2—C12	−0.1 (4)
C2—C3—C4—C5	2.7 (4)	C8—C7—N2—Cu1	179.4 (2)
C6—C3—C4—C5	−176.8 (3)	N1ⁱ—Cu1—N2—C12	109.81 (19)
C3—C4—C5—N1	0.1 (5)	N1—Cu1—N2—C12	−70.19 (19)
N2—C7—C8—C9	−0.7 (5)	O1—Cu1—N2—C12	19.53 (19)
C7—C8—C9—C11	1.5 (4)	O1ⁱ—Cu1—N2—C12	−160.47 (19)
C7—C8—C9—C10	−178.2 (3)	N1ⁱ—Cu1—N2—C7	−69.7 (2)
C8—C9—C11—C12	−1.5 (4)	N1—Cu1—N2—C7	110.3 (2)
C10—C9—C11—C12	178.3 (3)	O1—Cu1—N2—C7	−160.0 (2)
C9—C11—C12—N2	0.7 (4)	O1ⁱ—Cu1—N2—C7	20.0 (2)
N3—C13—C14—C15	0.1 (4)	C16—C17—N3—C13	1.0 (5)
C13—C14—C15—C16	1.2 (4)	C16—C17—N3—Cu2	−179.6 (3)
C13—C14—C15—C18	−179.7 (3)	C14—C13—N3—C17	−1.2 (4)
C14—C15—C16—C17	−1.4 (5)	C14—C13—N3—Cu2	179.34 (19)
C18—C15—C16—C17	179.4 (3)	N4ⁱⁱ—Cu2—N3—C17	109.5 (2)
C15—C16—C17—N3	0.4 (5)	N4—Cu2—N3—C17	−70.5 (2)
N4—C19—C20—C21	0.1 (4)	N4ⁱⁱ—Cu2—N3—C13	−71.1 (2)
C19—C20—C21—C22	1.6 (4)	N4—Cu2—N3—C13	108.9 (2)
C19—C20—C21—C24	−177.5 (3)	C22—C23—N4—C19	2.9 (4)
C20—C21—C22—C23	−1.1 (4)	C22—C23—N4—Cu2	−174.0 (2)
C24—C21—C22—C23	178.1 (3)	C20—C19—N4—C23	−2.3 (4)
C21—C22—C23—N4	−1.2 (5)	C20—C19—N4—Cu2	174.7 (2)
C2—C1—N1—C5	3.2 (4)	N3—Cu2—N4—C23	71.8 (2)
C2—C1—N1—Cu1	−174.3 (2)	N3ⁱⁱ—Cu2—N4—C23	−108.2 (2)
C4—C5—N1—C1	−3.1 (4)	N3—Cu2—N4—C19	−105.1 (2)
C4—C5—N1—Cu1	174.3 (2)	N3ⁱⁱ—Cu2—N4—C19	74.9 (2)
N2—Cu1—N1—C1	−73.2 (2)	N1ⁱ—Cu1—O1—S3	97.0 (7)
N2ⁱ—Cu1—N1—C1	106.8 (2)	N1—Cu1—O1—S3	−83.0 (7)
O1—Cu1—N1—C1	−163.6 (2)	N2—Cu1—O1—S3	−171.7 (7)
O1ⁱ—Cu1—N1—C1	16.4 (2)	N2ⁱ—Cu1—O1—S3	8.3 (7)
N2—Cu1—N1—C5	109.4 (2)	Cu1—O1—S3—O2	−173.0 (7)
N2ⁱ—Cu1—N1—C5	−70.6 (2)	Cu1—O1—S3—O3	−52.3 (7)
O1—Cu1—N1—C5	19.1 (2)	Cu1—O1—S3—O4	67.4 (7)
O1ⁱ—Cu1—N1—C5	−160.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱⁱⁱ	0.85	2.04	2.887 (4)	173
O5—H5B···O4^iv	0.85	2.01	2.843 (4)	168
O6—H6A···O6ⁱⁱⁱ	0.84	2.34	2.983 (6)	133
O6—H6B···O4^iv	0.85	1.92	2.762 (4)	172
O6—H6C···O8	0.85	1.98	2.804 (5)	163
O7—H7A···O5	0.84	2.16	2.906 (4)	148
O7—H7B···O3^v	0.85	2.13	2.923 (4)	157
O8—H8A···O3^iv	0.84	2.42	2.788 (4)	107
O8—H8B···O6	0.85	2.04	2.804 (5)	149
O8—H8C···O8^vi	0.85	1.87	2.710 (7)	176
O9—H9A···O6	0.84	2.48	3.210 (7)	145
O9—H9B···O3^iv	0.84	2.22	3.063 (7)	175
O9—H9B···O4^iv	0.84	2.71	3.275 (7)	126

Symmetry codes: (iii) −x+1, −y+1, −z; (iv) x, y−1, z; (v) x+1, y−1, z; (vi) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(C₆H₇N)₄]·4.393H₂O
M_r	611.27
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.4688 (12), 11.6327 (14), 12.8300 (15)
α, β, γ (°)	78.672 (3), 87.609 (3), 67.571 (3)
V (Å³)	1415.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.60 × 0.45 × 0.40

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (TWINABS; Bruker, 2008)
T_min, T_max	0.607, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	16814, 6963, 6170
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.118, 1.06
No. of reflections	6963
No. of parameters	361
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.61

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2009), CELL NOW (Bruker, 2009) and SAINT, SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6ⁱ	0.85	2.04	2.887 (4)	173
O5—H5B···O4ⁱⁱ	0.85	2.01	2.843 (4)	168
O6—H6A···O6ⁱ	0.84	2.34	2.983 (6)	133
O6—H6B···O4ⁱⁱ	0.85	1.92	2.762 (4)	172
O6—H6C···O8	0.85	1.98	2.804 (5)	163
O7—H7A···O5	0.84	2.16	2.906 (4)	148
O7—H7B···O3ⁱⁱⁱ	0.85	2.13	2.923 (4)	157
O8—H8A···O3ⁱⁱ	0.84	2.42	2.788 (4)	107
O8—H8B···O6	0.85	2.04	2.804 (5)	149
O8—H8C···O8^iv	0.85	1.87	2.710 (7)	176
O9—H9A···O6	0.84	2.48	3.210 (7)	145
O9—H9B···O3ⁱⁱ	0.84	2.22	3.063 (7)	175
O9—H9B···O4ⁱⁱ	0.84	2.71	3.275 (7)	126

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

Acknowledgements

We are thankful to the Higher Education Commission of Pakistan for funding. The X-ray diffractometer was funded by NSF grant 0087210, Ohio Board of Regents grant CAP-491 and Youngstown State University.

References

Bruker (2002). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). CELL NOW and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
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