metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 3| March 2011| Pages m375-m376

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

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[Shahid, M., Mazhar, M., Helliwell, M., Akhtar, J. & Ahmad, K. (2008). Acta Cryst. E64, m1139-m1140.], 2009[Shahid, M., Mazhar, M., O'Brien, P., Afzaal, M. & Raftery, J. (2009). Acta Cryst. E65, m163-m164.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(SO4)(C6H7N)4]·4.393H2O

  • Mr = 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[Bruker (2008). CELL NOW and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.607, Tmax = 0.746

  • 16814 measured reflections

  • 6963 independent reflections

  • 6170 reflections with I > 2σ(I)

  • Rint = 0.033

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.118

  • S = 1.06

  • 6963 reflections

  • 361 parameters

  • H-atom parameters constrained

  • Δρmax = 0.68 e Å−3

  • Δρmin = −0.61 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯O8iv 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[Bruker (2002). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: CELL NOW (Bruker, 2009[Bruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) and SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2008[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.]); software used to prepare material for publication: SHELXTL.

Supporting information


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)%.

Refinement top

The crystal under investigation was found to be non-merohedrally twinned by a 180° rotation around the reciprocal b-axis. The orientation matrices for the two components were identified using the program CELL NOW (Bruker, 2008), and the two components were integrated using SAINT, resulting in a total of 23387 reflections. 6633 reflections (4611 unique ones) involved component 1 only (mean I/σ = 12.2), 6573 reflections (3653 unique ones) involved component 2 only (mean I/σ = 5.8), and 10181 reflections (5801 unique ones) involved both components (mean I/σ = 9.4). The exact twin matrix identified by the integration program was found to be -1.00018 0.00039 0.00025, -0.83074 0.99991 - 0.32879, 0.00016 - 0.00153 - 0.99973. The structure was solved using direct methods with only the non-overlapping reflections of component 1. The structure was refined using the HKLF5 routine with all reflections of component 1 (including the overlapping ones) below a d-spacing threshold of 0.75 Å, resulting in a BASF value of 0.211 (1). The Rint value given is for all reflections before the cutoff at d = 0.75 Å and is based on agreement between observed single and composite intensities and those calculated from refined unique intensities and twin fractions (TWINABS; Bruker, 2008).

Hydrogen atoms of the water molecules are partially disordered over mutually exclusive positions due to hydrogen bonding between symmetry equivalent water molecules across inversion centers. The H atoms in question are H6A and H8C, which are each located close to a crystallographic inversion center between pairs of symmetry equivalent atoms of O6 and O8. Both H atoms were thus refined as 50% occupied. For both water molecules O6 and O8 a second half occupied hydrogen atom is located in a position in which it hydrogen-bonds with the a neighboring water molecule of O8 and O6, respectively, thus again creating a pair of close by half occupied H atoms (H6C and H8B) in mutually exclusive positions. The water solvate molecule of O9 is only partially occupied with a refined occupancy factor of 0.396 (4). Water hydrogen atoms were located in difference density Fourier maps, assigned occupancies as described above and their positions were refined with an O—H distance of 0.84 (1) Å and H···H distances of 1.30 (1) Å. In the final refinement cycles the water H atoms were set to ride on their carrying oxygen atoms. All other hydrogen atoms were immediately placed in calculated positions and all H atoms were refined with an isotropic displacement parameter Uiso of 1.5 (methyl, hydroxyl) or 1.2 times (aromatic) that of Ueq of the adjacent carbon or oxygen atom.

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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]·4.393H2OZ = 2
Mr = 611.27F(000) = 642
Triclinic, P1Dx = 1.434 Mg m3
Hall symbol: -P 1Melting point: 373 K
a = 10.4688 (12) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.6327 (14) ÅCell parameters from 4676 reflections
c = 12.8300 (15) Åθ = 2.3–30.4°
α = 78.672 (3)°µ = 0.90 mm1
β = 87.609 (3)°T = 100 K
γ = 67.571 (3)°Block, blue
V = 1415.2 (3) Å30.60 × 0.45 × 0.40 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
6963 independent reflections
Radiation source: fine-focus sealed tube6170 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan
(TWINABS; Bruker, 2008)
h = 1313
Tmin = 0.607, Tmax = 0.746k = 1515
16814 measured reflectionsl = 017
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0573P)2 + 1.4896P]
where P = (Fo2 + 2Fc2)/3
6963 reflections(Δ/σ)max < 0.001
361 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = 0.61 e Å3
Crystal data top
[Cu(SO4)(C6H7N)4]·4.393H2Oγ = 67.571 (3)°
Mr = 611.27V = 1415.2 (3) Å3
Triclinic, P1Z = 2
a = 10.4688 (12) ÅMo Kα radiation
b = 11.6327 (14) ŵ = 0.90 mm1
c = 12.8300 (15) ÅT = 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)
Tmin = 0.607, Tmax = 0.746Rint = 0.033
16814 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.06Δρmax = 0.68 e Å3
6963 reflectionsΔρmin = 0.61 e Å3
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
xyzUiso*/UeqOcc. (<1)
C10.7599 (3)1.0000 (3)0.5809 (2)0.0204 (5)
H10.75940.92630.62810.024*
C20.8641 (3)1.0426 (3)0.5935 (2)0.0231 (5)
H20.93290.99840.64880.028*
C30.8680 (3)1.1497 (3)0.5255 (2)0.0230 (5)
C40.7680 (3)1.2070 (3)0.4436 (2)0.0254 (6)
H40.76921.27840.39320.030*
C50.6665 (3)1.1597 (3)0.4355 (2)0.0242 (6)
H50.59901.19990.37890.029*
C60.9755 (3)1.2030 (3)0.5399 (3)0.0313 (6)
H6F0.93381.27750.57290.047*
H6E1.01001.22780.47040.047*
H6D1.05231.13850.58560.047*
C70.6771 (3)0.7248 (3)0.5052 (2)0.0259 (6)
H70.64530.71250.57540.031*
C80.7656 (4)0.6209 (3)0.4678 (2)0.0318 (7)
H80.79430.53920.51230.038*
C90.8136 (3)0.6346 (3)0.3647 (2)0.0272 (6)
C100.9073 (4)0.5230 (3)0.3195 (3)0.0451 (9)
H10A0.85480.47360.30500.068*
H10B0.98340.46950.37090.068*
H10C0.94490.55320.25330.068*
C110.7700 (3)0.7568 (3)0.3053 (2)0.0224 (5)
H110.80150.77150.23530.027*
C120.6808 (3)0.8575 (3)0.3476 (2)0.0212 (5)
H120.65170.94020.30480.025*
C130.4334 (3)0.8651 (3)0.2020 (2)0.0216 (5)
H130.38700.94900.21380.026*
C140.4296 (3)0.7646 (3)0.2792 (2)0.0208 (5)
H140.38110.78060.34240.025*
C150.4963 (3)0.6413 (3)0.2645 (2)0.0253 (6)
C160.5674 (4)0.6247 (3)0.1714 (2)0.0341 (7)
H160.61660.54160.15850.041*
C170.5667 (3)0.7287 (3)0.0975 (2)0.0310 (6)
H170.61560.71500.03420.037*
C180.4934 (4)0.5303 (3)0.3466 (2)0.0371 (8)
H18A0.57350.50000.39600.056*
H18B0.49670.46200.31120.056*
H18C0.40820.55690.38600.056*
C190.7394 (3)1.0233 (3)0.0928 (2)0.0228 (5)
H190.66921.09670.11050.027*
C200.8748 (3)0.9916 (3)0.1272 (2)0.0258 (6)
H200.89581.04280.16760.031*
C210.9792 (3)0.8852 (3)0.1023 (2)0.0256 (6)
C220.9428 (3)0.8158 (3)0.0406 (2)0.0291 (6)
H221.01130.74300.02070.035*
C230.8054 (3)0.8539 (3)0.0084 (2)0.0272 (6)
H230.78220.80670.03490.033*
C241.1264 (3)0.8448 (3)0.1420 (2)0.0328 (7)
H24A1.14780.92010.14050.049*
H24B1.18930.79180.09620.049*
H24C1.13780.79640.21500.049*
Cu10.50001.00000.50000.01857 (11)
Cu20.50001.00000.00000.02031 (11)
N10.6596 (2)1.0589 (2)0.50462 (17)0.0197 (4)
N20.6332 (2)0.8438 (2)0.44667 (17)0.0196 (4)
N30.5002 (2)0.8479 (2)0.11114 (17)0.0204 (4)
N40.7039 (2)0.9544 (2)0.03565 (17)0.0208 (4)
O10.4432 (2)1.11465 (19)0.32076 (14)0.0241 (4)
O20.4297 (2)1.1372 (2)0.13099 (15)0.0257 (4)
O30.2438 (2)1.2743 (2)0.21897 (18)0.0387 (6)
O40.4641 (3)1.2969 (2)0.20710 (19)0.0389 (6)
O50.7247 (3)0.3043 (2)0.1438 (2)0.0501 (7)
H5A0.70070.35190.08260.075*
H5B0.65290.29560.17140.075*
O60.3674 (3)0.5172 (3)0.0548 (2)0.0568 (7)
H6A0.41030.50110.00080.085*0.50
H6B0.40340.44670.09720.085*
H6C0.29050.51470.03990.085*0.50
O70.9960 (3)0.2146 (3)0.2479 (2)0.0567 (8)
H7A0.92930.26320.20540.085*
H7B1.05520.24490.22280.085*
O80.1306 (4)0.4630 (4)0.0397 (4)0.0971 (15)
H8A0.11090.47220.10270.146*
H8B0.18420.50270.02610.146*0.50
H8C0.05070.48440.01250.146*0.50
O90.2000 (7)0.5327 (6)0.2704 (5)0.045 (2)0.393 (8)
H9A0.23110.56400.21510.067*0.393 (8)
H9B0.21660.45930.25900.067*0.393 (8)
S30.39467 (7)1.20521 (6)0.21937 (5)0.01904 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0229 (13)0.0205 (12)0.0186 (12)0.0087 (11)0.0004 (9)0.0046 (10)
C20.0201 (12)0.0294 (14)0.0220 (13)0.0095 (11)0.0012 (10)0.0099 (11)
C30.0187 (12)0.0275 (14)0.0274 (14)0.0106 (11)0.0047 (10)0.0131 (11)
C40.0276 (14)0.0269 (14)0.0247 (14)0.0145 (12)0.0019 (11)0.0035 (11)
C50.0278 (14)0.0285 (14)0.0198 (13)0.0162 (12)0.0028 (10)0.0002 (10)
C60.0259 (14)0.0341 (16)0.0411 (17)0.0166 (13)0.0008 (12)0.0126 (13)
C70.0371 (16)0.0245 (14)0.0176 (12)0.0145 (12)0.0017 (11)0.0015 (10)
C80.0478 (19)0.0231 (14)0.0235 (14)0.0138 (14)0.0010 (13)0.0013 (11)
C90.0316 (15)0.0267 (15)0.0241 (14)0.0111 (12)0.0026 (11)0.0056 (11)
C100.062 (2)0.0287 (17)0.0363 (19)0.0067 (17)0.0047 (17)0.0091 (14)
C110.0238 (13)0.0278 (14)0.0184 (12)0.0128 (11)0.0005 (10)0.0046 (10)
C120.0202 (12)0.0258 (13)0.0190 (12)0.0118 (11)0.0009 (10)0.0014 (10)
C130.0212 (13)0.0235 (13)0.0222 (13)0.0106 (11)0.0007 (10)0.0044 (10)
C140.0221 (12)0.0275 (14)0.0178 (12)0.0145 (11)0.0002 (10)0.0051 (10)
C150.0333 (15)0.0262 (14)0.0187 (13)0.0148 (12)0.0032 (11)0.0017 (10)
C160.053 (2)0.0220 (14)0.0234 (14)0.0103 (14)0.0054 (13)0.0057 (11)
C170.0429 (18)0.0297 (15)0.0183 (13)0.0117 (14)0.0062 (12)0.0053 (11)
C180.062 (2)0.0293 (16)0.0227 (15)0.0231 (16)0.0065 (14)0.0013 (12)
C190.0259 (13)0.0262 (14)0.0201 (12)0.0157 (11)0.0012 (10)0.0010 (10)
C200.0290 (14)0.0341 (15)0.0208 (13)0.0211 (13)0.0035 (10)0.0006 (11)
C210.0212 (13)0.0377 (16)0.0175 (12)0.0147 (12)0.0016 (10)0.0032 (11)
C220.0232 (14)0.0358 (16)0.0252 (14)0.0078 (12)0.0004 (11)0.0059 (12)
C230.0280 (14)0.0338 (15)0.0223 (13)0.0134 (13)0.0044 (11)0.0065 (12)
C240.0235 (14)0.0469 (18)0.0278 (15)0.0162 (14)0.0024 (11)0.0009 (13)
Cu10.0212 (2)0.0220 (2)0.0169 (2)0.01266 (19)0.00015 (16)0.00454 (18)
Cu20.0198 (2)0.0240 (2)0.0176 (2)0.0110 (2)0.00355 (16)0.00135 (18)
N10.0229 (11)0.0248 (11)0.0158 (10)0.0127 (9)0.0005 (8)0.0060 (8)
N20.0237 (11)0.0233 (11)0.0163 (10)0.0141 (9)0.0028 (8)0.0025 (8)
N30.0213 (11)0.0236 (11)0.0178 (10)0.0103 (9)0.0041 (8)0.0027 (9)
N40.0221 (11)0.0242 (11)0.0172 (10)0.0119 (9)0.0015 (8)0.0003 (8)
O10.0311 (10)0.0295 (10)0.0130 (8)0.0145 (9)0.0030 (7)0.0002 (7)
O20.0331 (11)0.0319 (11)0.0149 (9)0.0143 (9)0.0015 (8)0.0069 (8)
O30.0250 (11)0.0461 (14)0.0315 (12)0.0004 (10)0.0011 (9)0.0046 (10)
O40.0571 (15)0.0289 (11)0.0373 (13)0.0282 (11)0.0223 (11)0.0077 (9)
O50.0516 (16)0.0386 (14)0.0540 (16)0.0131 (12)0.0121 (13)0.0011 (12)
O60.077 (2)0.0500 (17)0.0409 (15)0.0260 (16)0.0023 (14)0.0007 (13)
O70.0577 (17)0.0562 (17)0.0492 (16)0.0260 (15)0.0123 (13)0.0174 (14)
O80.066 (2)0.089 (3)0.123 (3)0.044 (2)0.044 (2)0.050 (2)
O90.049 (4)0.044 (4)0.045 (4)0.017 (3)0.001 (3)0.017 (3)
S30.0231 (3)0.0207 (3)0.0147 (3)0.0099 (2)0.0032 (2)0.0026 (2)
Geometric parameters (Å, º) top
C1—N11.343 (3)C19—N41.342 (3)
C1—C21.386 (4)C19—C201.388 (4)
C1—H10.9500C19—H190.9500
C2—C31.387 (4)C20—C211.386 (4)
C2—H20.9500C20—H200.9500
C3—C41.389 (4)C21—C221.391 (4)
C3—C61.509 (4)C21—C241.508 (4)
C4—C51.386 (4)C22—C231.388 (4)
C4—H40.9500C22—H220.9500
C5—N11.348 (4)C23—N41.341 (4)
C5—H50.9500C23—H230.9500
C6—H6F0.9800C24—H24A0.9800
C6—H6E0.9800C24—H24B0.9800
C6—H6D0.9800C24—H24C0.9800
C7—N21.352 (4)Cu1—N1i2.041 (2)
C7—C81.373 (4)Cu1—N12.041 (2)
C7—H70.9500Cu1—N22.046 (2)
C8—C91.397 (4)Cu1—N2i2.046 (2)
C8—H80.9500Cu1—O12.3926 (18)
C9—C111.385 (4)Cu1—O1i2.3926 (18)
C9—C101.503 (4)Cu2—N4ii2.042 (2)
C10—H10A0.9800Cu2—N42.042 (2)
C10—H10B0.9800Cu2—N32.042 (2)
C10—H10C0.9800Cu2—N3ii2.042 (2)
C11—C121.382 (4)Cu2—O2ii2.443 (2)
C11—H110.9500Cu2—O22.443 (2)
C12—N21.348 (3)O1—S31.4726 (19)
C12—H120.9500O2—S31.464 (2)
C13—N31.344 (3)O3—S31.473 (2)
C13—C141.387 (4)O4—S31.485 (2)
C13—H130.9500O5—H5A0.8515
C14—C151.382 (4)O5—H5B0.8498
C14—H140.9500O6—H6A0.8408
C15—C161.388 (4)O6—H6B0.8470
C15—C181.507 (4)O6—H6C0.8472
C16—C171.381 (4)O7—H7A0.8445
C16—H160.9500O7—H7B0.8477
C17—N31.336 (4)O8—H8A0.8431
C17—H170.9500O8—H8B0.8459
C18—H18A0.9800O8—H8C0.8456
C18—H18B0.9800O9—H9A0.8436
C18—H18C0.9800O9—H9B0.8448
N1—C1—C2122.6 (3)C22—C21—C24121.1 (3)
N1—C1—H1118.7C23—C22—C21119.3 (3)
C2—C1—H1118.7C23—C22—H22120.3
C1—C2—C3120.0 (3)C21—C22—H22120.3
C1—C2—H2120.0N4—C23—C22123.0 (3)
C3—C2—H2120.0N4—C23—H23118.5
C2—C3—C4117.3 (2)C22—C23—H23118.5
C2—C3—C6121.7 (3)C21—C24—H24A109.5
C4—C3—C6121.0 (3)C21—C24—H24B109.5
C5—C4—C3119.7 (3)H24A—C24—H24B109.5
C5—C4—H4120.1C21—C24—H24C109.5
C3—C4—H4120.1H24A—C24—H24C109.5
N1—C5—C4122.7 (3)H24B—C24—H24C109.5
N1—C5—H5118.7N1i—Cu1—N1180.00 (11)
C4—C5—H5118.7N1i—Cu1—N291.28 (9)
C3—C6—H6F109.5N1—Cu1—N288.72 (9)
C3—C6—H6E109.5N1i—Cu1—N2i88.72 (9)
H6F—C6—H6E109.5N1—Cu1—N2i91.28 (9)
C3—C6—H6D109.5N2—Cu1—N2i179.999 (1)
H6F—C6—H6D109.5N1i—Cu1—O190.27 (8)
H6E—C6—H6D109.5N1—Cu1—O189.73 (8)
N2—C7—C8122.9 (3)N2—Cu1—O190.38 (8)
N2—C7—H7118.5N2i—Cu1—O189.62 (8)
C8—C7—H7118.5N1i—Cu1—O1i89.73 (8)
C7—C8—C9120.4 (3)N1—Cu1—O1i90.27 (8)
C7—C8—H8119.8N2—Cu1—O1i89.62 (8)
C9—C8—H8119.8N2i—Cu1—O1i90.38 (8)
C11—C9—C8116.6 (3)O1—Cu1—O1i180.0
C11—C9—C10121.3 (3)N4ii—Cu2—N4180.0
C8—C9—C10122.1 (3)N4ii—Cu2—N389.63 (9)
C9—C10—H10A109.5N4—Cu2—N390.37 (9)
C9—C10—H10B109.5N4ii—Cu2—N3ii90.37 (9)
H10A—C10—H10B109.5N4—Cu2—N3ii89.63 (9)
C9—C10—H10C109.5N3—Cu2—N3ii179.999 (1)
H10A—C10—H10C109.5N4—Cu2—O2ii88.90 (8)
H10B—C10—H10C109.5N4ii—Cu2—O2ii91.11 (8)
C12—C11—C9120.2 (3)N3—Cu2—O2ii88.72 (8)
C12—C11—H11119.9N3ii—Cu2—O2ii91.28 (8)
C9—C11—H11119.9N4—Cu2—O291.11 (8)
N2—C12—C11123.1 (3)N4ii—Cu2—O288.90 (8)
N2—C12—H12118.5N3—Cu2—O291.28 (8)
C11—C12—H12118.5N3ii—Cu2—O288.72 (8)
N3—C13—C14122.4 (3)O2ii—Cu2—O2180.000 (1)
N3—C13—H13118.8C1—N1—C5117.5 (2)
C14—C13—H13118.8C1—N1—Cu1120.11 (18)
C15—C14—C13120.2 (3)C5—N1—Cu1122.30 (18)
C15—C14—H14119.9C12—N2—C7116.8 (2)
C13—C14—H14119.9C12—N2—Cu1119.50 (19)
C14—C15—C16116.9 (3)C7—N2—Cu1123.72 (19)
C14—C15—C18121.5 (3)C17—N3—C13117.5 (2)
C16—C15—C18121.7 (3)C17—N3—Cu2122.05 (19)
C17—C16—C15120.1 (3)C13—N3—Cu2120.41 (19)
C17—C16—H16120.0C23—N4—C19117.7 (2)
C15—C16—H16120.0C23—N4—Cu2122.75 (19)
N3—C17—C16122.9 (3)C19—N4—Cu2119.52 (19)
N3—C17—H17118.5S3—O1—Cu1169.60 (13)
C16—C17—H17118.5H5A—O5—H5B107.6
C15—C18—H18A109.5H6A—O6—H6B101.2
C15—C18—H18B109.5H6A—O6—H6C101.0
H18A—C18—H18B109.5H6B—O6—H6C100.4
C15—C18—H18C109.5H7A—O7—H7B97.7
H18A—C18—H18C109.5H8A—O8—H8B100.6
H18B—C18—H18C109.5H8A—O8—H8C100.5
N4—C19—C20122.5 (3)H8B—O8—H8C126.9
N4—C19—H19118.7H9A—O9—H9B100.6
C20—C19—H19118.7O2—S3—O1109.72 (12)
C21—C20—C19119.9 (3)O2—S3—O3109.57 (13)
C21—C20—H20120.0O1—S3—O3110.06 (13)
C19—C20—H20120.0O2—S3—O4109.34 (14)
C20—C21—C22117.5 (3)O1—S3—O4108.76 (12)
C20—C21—C24121.4 (3)O3—S3—O4109.37 (15)
N1—C1—C2—C30.3 (4)C11—C12—N2—C70.1 (4)
C1—C2—C3—C42.6 (4)C11—C12—N2—Cu1179.4 (2)
C1—C2—C3—C6176.9 (3)C8—C7—N2—C120.1 (4)
C2—C3—C4—C52.7 (4)C8—C7—N2—Cu1179.4 (2)
C6—C3—C4—C5176.8 (3)N1i—Cu1—N2—C12109.81 (19)
C3—C4—C5—N10.1 (5)N1—Cu1—N2—C1270.19 (19)
N2—C7—C8—C90.7 (5)O1—Cu1—N2—C1219.53 (19)
C7—C8—C9—C111.5 (4)O1i—Cu1—N2—C12160.47 (19)
C7—C8—C9—C10178.2 (3)N1i—Cu1—N2—C769.7 (2)
C8—C9—C11—C121.5 (4)N1—Cu1—N2—C7110.3 (2)
C10—C9—C11—C12178.3 (3)O1—Cu1—N2—C7160.0 (2)
C9—C11—C12—N20.7 (4)O1i—Cu1—N2—C720.0 (2)
N3—C13—C14—C150.1 (4)C16—C17—N3—C131.0 (5)
C13—C14—C15—C161.2 (4)C16—C17—N3—Cu2179.6 (3)
C13—C14—C15—C18179.7 (3)C14—C13—N3—C171.2 (4)
C14—C15—C16—C171.4 (5)C14—C13—N3—Cu2179.34 (19)
C18—C15—C16—C17179.4 (3)N4ii—Cu2—N3—C17109.5 (2)
C15—C16—C17—N30.4 (5)N4—Cu2—N3—C1770.5 (2)
N4—C19—C20—C210.1 (4)N4ii—Cu2—N3—C1371.1 (2)
C19—C20—C21—C221.6 (4)N4—Cu2—N3—C13108.9 (2)
C19—C20—C21—C24177.5 (3)C22—C23—N4—C192.9 (4)
C20—C21—C22—C231.1 (4)C22—C23—N4—Cu2174.0 (2)
C24—C21—C22—C23178.1 (3)C20—C19—N4—C232.3 (4)
C21—C22—C23—N41.2 (5)C20—C19—N4—Cu2174.7 (2)
C2—C1—N1—C53.2 (4)N3—Cu2—N4—C2371.8 (2)
C2—C1—N1—Cu1174.3 (2)N3ii—Cu2—N4—C23108.2 (2)
C4—C5—N1—C13.1 (4)N3—Cu2—N4—C19105.1 (2)
C4—C5—N1—Cu1174.3 (2)N3ii—Cu2—N4—C1974.9 (2)
N2—Cu1—N1—C173.2 (2)N1i—Cu1—O1—S397.0 (7)
N2i—Cu1—N1—C1106.8 (2)N1—Cu1—O1—S383.0 (7)
O1—Cu1—N1—C1163.6 (2)N2—Cu1—O1—S3171.7 (7)
O1i—Cu1—N1—C116.4 (2)N2i—Cu1—O1—S38.3 (7)
N2—Cu1—N1—C5109.4 (2)Cu1—O1—S3—O2173.0 (7)
N2i—Cu1—N1—C570.6 (2)Cu1—O1—S3—O352.3 (7)
O1—Cu1—N1—C519.1 (2)Cu1—O1—S3—O467.4 (7)
O1i—Cu1—N1—C5160.9 (2)
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O6iii0.852.042.887 (4)173
O5—H5B···O4iv0.852.012.843 (4)168
O6—H6A···O6iii0.842.342.983 (6)133
O6—H6B···O4iv0.851.922.762 (4)172
O6—H6C···O80.851.982.804 (5)163
O7—H7A···O50.842.162.906 (4)148
O7—H7B···O3v0.852.132.923 (4)157
O8—H8A···O3iv0.842.422.788 (4)107
O8—H8B···O60.852.042.804 (5)149
O8—H8C···O8vi0.851.872.710 (7)176
O9—H9A···O60.842.483.210 (7)145
O9—H9B···O3iv0.842.223.063 (7)175
O9—H9B···O4iv0.842.713.275 (7)126
Symmetry codes: (iii) x+1, y+1, z; (iv) x, y1, z; (v) x+1, y1, z; (vi) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu(SO4)(C6H7N)4]·4.393H2O
Mr611.27
Crystal system, space groupTriclinic, 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)
V3)1415.2 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.90
Crystal size (mm)0.60 × 0.45 × 0.40
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(TWINABS; Bruker, 2008)
Tmin, Tmax0.607, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
16814, 6963, 6170
Rint0.033
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.118, 1.06
No. of reflections6963
No. of parameters361
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O5—H5A···O6i0.852.042.887 (4)173
O5—H5B···O4ii0.852.012.843 (4)168
O6—H6A···O6i0.842.342.983 (6)133
O6—H6B···O4ii0.851.922.762 (4)172
O6—H6C···O80.851.982.804 (5)163
O7—H7A···O50.842.162.906 (4)148
O7—H7B···O3iii0.852.132.923 (4)157
O8—H8A···O3ii0.842.422.788 (4)107
O8—H8B···O60.852.042.804 (5)149
O8—H8C···O8iv0.851.872.710 (7)176
O9—H9A···O60.842.483.210 (7)145
O9—H9B···O3ii0.842.223.063 (7)175
O9—H9B···O4ii0.842.713.275 (7)126
Symmetry codes: (i) x+1, y+1, z; (ii) x, y1, z; (iii) x+1, y1, 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

First citationBruker (2002). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2008). CELL NOW and TWINABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2009). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationMacrae, 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
First citationShahid, M., Mazhar, M., Helliwell, M., Akhtar, J. & Ahmad, K. (2008). Acta Cryst. E64, m1139–m1140.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationShahid, M., Mazhar, M., O'Brien, P., Afzaal, M. & Raftery, J. (2009). Acta Cryst. E65, m163–m164.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
Volume 67| Part 3| March 2011| Pages m375-m376
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