Bromidobis(N,N′-diphenyl­thio­urea-κS)copper(I) monohydrate

Mufakkar, M.; Tahir, M.N.; Ahmad, S.; Shaheen, M.A.; Waheed, A.

doi:10.1107/S1600536809026038

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m892-m893

doi:10.1107/S1600536809026038

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Bromidobis(N,N′-diphenylthiourea-κS)copper(I) monohydrate

Muhammad Mufakkar,^a M. Nawaz Tahir,^b ^* Saeed Ahmad,^c Muhammad Ashraf Shaheen ^d and Abdul Waheed ^a

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, ^cDepartment of Chemistry, University of Engineering and Technology, Lahore, Pakistan, and ^dDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 4 July 2009; accepted 4 July 2009; online 11 July 2009)

In the title compound, [CuBr(C₁₃H₁₂N₂S)₂]·H₂O, the Cu^I atom adopts a slightly distorted trigonal-planar coordination arising from two S atoms of two diphenylthiourea ligands and a bromide ion. There are two intramolecular N—H⋯Br hydrogen bonds completing twisted six-membered rings with R(6) motifs. The dihedral angles between the aromatic rings in the ligands are 62.11 (13) and 85.73 (13)°. In the crystal, components are linked by N—H⋯O, O—H⋯S and O—H⋯π interactions. There also exist π–π interactions with a distance of 3.876 (2) Å between the centroids of benzene rings of two different ligands. Together, the intermolecular interactions lead to a three-dimensional network.

Related literature

For related structures, see: Khan et al. (2007 ); Mufakkar et al. (2007 ); Zoufalá et al. (2007 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

[CuBr(C₁₃H₁₂N₂S)₂]·H₂O
M_r = 618.08
Triclinic, $[P \overline 1]$
a = 9.6195 (5) Å
b = 12.1937 (6) Å
c = 12.7969 (6) Å
α = 89.345 (2)°
β = 73.154 (1)°
γ = 69.225 (2)°
V = 1336.20 (11) Å³
Z = 2
Mo Kα radiation
μ = 2.50 mm⁻¹
T = 296 K
0.28 × 0.23 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.509, T_max = 0.606
27804 measured reflections
6568 independent reflections
5426 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.122
S = 1.04
6568 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—Br1	2.3387 (5)
Cu1—S1	2.2263 (8)
Cu1—S2	2.2129 (8)

Br1—Cu1—S1	125.03 (3)
Br1—Cu1—S2	126.04 (3)
S1—Cu1—S2	108.93 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.86	2.35	3.046 (4)	139
O1—H1O⋯S1ⁱⁱ	0.83	2.66	3.462 (3)	163
N2—H2N⋯Br1	0.86	2.59	3.435 (2)	169
N3—H3N⋯O1ⁱⁱⁱ	0.86	2.16	2.957 (3)	155
N4—H4N⋯Br1	0.86	2.72	3.573 (2)	170
C13—H13⋯N1	0.93	2.58	3.000 (4)	108
C13—H13⋯S2^iv	0.93	2.86	3.523 (3)	129
O1—H2O⋯CgDⁱⁱⁱ	0.80	2.78	3.306 (3)	125
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y+1, z; (iii) -x+1, -y+1, -z; (iv) -x+1, -y, -z+1. CgD is the centroid of the C21–C26 benzene ring.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026038/hb5021sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026038/hb5021Isup2.hkl

checkCIF report

Comment top

The crystal structure of tetrakis(N-methylthiourea-S)copper(I) iodide (Mufakkar et al., 2007)), tris(N,N'-dibutylthiourea-S)iodidocopper(I) 0.6-hydrate (Khan et al., 2007) and tetrakis(N-methylthiourea)copper(I) chloride (Zoufalá et al., 2007) have been reported by our group containing substituted thiourea. In continuation to the copper complexes of substituted thiourea, the title compound (I), (Fig. 1) is now reported.

In (I), the copper atom is coordinated to two S-atoms of two diphenylthiourea ligands and the Br-atom. Cu1 is at a distance of -0.0061 (5) Å from the plane of S1/S2/BR1. In one ligand the benzene rings A (C2—C7) and B (C8—C13) make a dihedral angle of 85.73 (13)°, whereas in the other ligand the benzene rings C (C15—C20) and D (C21—C26) are oriented at dihedral angle of 62.11 (13)°. There exist two intramolecular H-bonds of N–H···Br type, completing two twisted six membered rings with ring motifs R₁¹(6) (Bernstein et al., 1995). The NH-groups not involving in H-bonding with Br-atom, make intermolecular H-bonds with O-atom of water. It is interesting that only one H-atom of water molecule make H-bonding with one of S-atom, whereas the other make a π interaction (Table 1). There exist π–π interactions between CgA···CgCⁱ [symmetry code: i = -1 + x, y, 1 + z] and CgC···CgAⁱⁱ [symmetry code: ii = 1 + x, y, -1 + z] at a distance of 3.876 (2) Å, where CgA and CgC are the centroids of benzene rings A and C, respectively. The molecules are linked each other through H-bonding in the form of three dimensional polymeric network.

Related literature top

For related structures, see: Khan et al. (2007); Mufakkar et al. (2007); Zoufalá et al. (2007). For graph-set notation, see: Bernstein et al. (1995). CgD is the centroid of the C21–C26 benzene ring.

Experimental top

Copper(I) bromide (0.14 g, 1.0 mmol) was dissolved in 15 ml of acetonitrile and it was added to two equivalents of N,N'-diphenylthiourea in acetonitrile. White precipitate formed immediately were filtered and the filtrate was kept for crystallization. As a result colourless prisms of (I) were obtained after 24 h.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 30% probability level. H-atoms are shown by small spheres of arbitrary radius.
	Fig. 2. The partial packing of (I), showing that molecules form ring motifs and form three dimensional polymeric network.

Bromidobis(N,N'-diphenylthiourea-κS)copper(I) monohydrate top

Crystal data top

[CuBr(C₁₃H₁₂N₂S)₂]·H₂O	Z = 2
M_r = 618.08	F(000) = 628
Triclinic, P1	D_x = 1.536 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6195 (5) Å	Cell parameters from 6568 reflections
b = 12.1937 (6) Å	θ = 2.3–28.3°
c = 12.7969 (6) Å	µ = 2.50 mm⁻¹
α = 89.345 (2)°	T = 296 K
β = 73.154 (1)°	Prismatic, colourless
γ = 69.225 (2)°	0.28 × 0.23 × 0.20 mm
V = 1336.20 (11) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	6568 independent reflections
Radiation source: fine-focus sealed tube	5426 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 7.40 pixels mm^-1	θ_max = 28.3°, θ_min = 2.3°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −16→16
T_min = 0.509, T_max = 0.606	l = −17→15
27804 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0609P)² + 1.6374P] where P = (F_o² + 2F_c²)/3
6568 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −1.27 e Å⁻³

Crystal data top

[CuBr(C₁₃H₁₂N₂S)₂]·H₂O	γ = 69.225 (2)°
M_r = 618.08	V = 1336.20 (11) Å³
Triclinic, P1	Z = 2
a = 9.6195 (5) Å	Mo Kα radiation
b = 12.1937 (6) Å	µ = 2.50 mm⁻¹
c = 12.7969 (6) Å	T = 296 K
α = 89.345 (2)°	0.28 × 0.23 × 0.20 mm
β = 73.154 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6568 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5426 reflections with I > 2σ(I)
T_min = 0.509, T_max = 0.606	R_int = 0.024
27804 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.04	Δρ_max = 0.47 e Å⁻³
6568 reflections	Δρ_min = −1.27 e Å⁻³
316 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Br1	0.33324 (5)	0.31120 (3)	0.30610 (3)	0.0533 (1)
Cu1	0.44586 (4)	0.10611 (3)	0.26717 (3)	0.0365 (1)
S1	0.38543 (9)	−0.02233 (6)	0.37916 (6)	0.0371 (2)
S2	0.62984 (9)	0.00799 (6)	0.11533 (5)	0.0363 (2)
N1	0.1849 (3)	−0.0049 (2)	0.57745 (18)	0.0329 (6)
N2	0.2381 (3)	0.1621 (2)	0.52856 (18)	0.0332 (7)
N3	0.7569 (3)	0.0539 (2)	−0.08459 (18)	0.0333 (6)
N4	0.5479 (3)	0.2083 (2)	0.02461 (19)	0.0340 (7)
C1	0.2624 (3)	0.0486 (2)	0.5043 (2)	0.0285 (7)
C2	0.2046 (3)	−0.1261 (2)	0.5679 (2)	0.0296 (7)
C3	0.0747 (4)	−0.1555 (3)	0.5850 (3)	0.0389 (9)
C4	0.0924 (5)	−0.2732 (3)	0.5780 (3)	0.0513 (11)
C5	0.2378 (5)	−0.3602 (3)	0.5535 (4)	0.0632 (13)
C6	0.3667 (5)	−0.3298 (3)	0.5391 (4)	0.0621 (13)
C7	0.3512 (4)	−0.2133 (3)	0.5473 (3)	0.0448 (10)
C8	0.1611 (3)	0.2336 (2)	0.6302 (2)	0.0312 (8)
C9	0.0889 (4)	0.3536 (3)	0.6266 (3)	0.0481 (10)
C10	0.0182 (5)	0.4277 (3)	0.7237 (3)	0.0619 (13)
C11	0.0184 (5)	0.3834 (3)	0.8227 (3)	0.0564 (11)
C12	0.0909 (4)	0.2642 (3)	0.8259 (3)	0.0449 (10)
C13	0.1640 (4)	0.1892 (3)	0.7301 (2)	0.0376 (8)
C14	0.6462 (3)	0.0959 (2)	0.0114 (2)	0.0284 (7)
C15	0.8697 (3)	−0.0636 (3)	−0.1082 (2)	0.0321 (7)
C16	0.8232 (4)	−0.1582 (3)	−0.1121 (3)	0.0410 (9)
C17	0.9331 (5)	−0.2719 (3)	−0.1320 (3)	0.0536 (11)
C18	1.0894 (4)	−0.2896 (3)	−0.1513 (3)	0.0552 (11)
C19	1.1351 (4)	−0.1968 (3)	−0.1499 (3)	0.0533 (10)
C20	1.0255 (3)	−0.0819 (3)	−0.1277 (3)	0.0413 (9)
C21	0.5400 (3)	0.2845 (2)	−0.0615 (2)	0.0337 (8)
C22	0.4526 (4)	0.2811 (3)	−0.1278 (3)	0.0557 (12)
C23	0.4443 (5)	0.3550 (4)	−0.2108 (4)	0.0703 (17)
C24	0.5207 (5)	0.4323 (3)	−0.2251 (3)	0.0628 (14)
C25	0.6103 (5)	0.4334 (4)	−0.1598 (4)	0.0647 (14)
C26	0.6218 (5)	0.3594 (3)	−0.0775 (3)	0.0514 (11)
O1	0.1532 (3)	0.8554 (2)	0.29920 (19)	0.0501 (8)
H1N	0.11673	0.03785	0.63566	0.0395*
H2N	0.27483	0.19654	0.47431	0.0399*
H3	−0.02407	−0.09678	0.60112	0.0466*
H3N	0.76077	0.10051	−0.13542	0.0399*
H4	0.00491	−0.29344	0.59005	0.0615*
H4N	0.48508	0.23679	0.08933	0.0408*
H5	0.24930	−0.43899	0.54660	0.0755*
H6	0.46526	−0.38872	0.52367	0.0746*
H7	0.43836	−0.19341	0.53904	0.0537*
H9	0.08789	0.38413	0.55980	0.0576*
H10	−0.02992	0.50831	0.72171	0.0742*
H11	−0.03026	0.43368	0.88744	0.0678*
H12	0.09072	0.23412	0.89305	0.0539*
H13	0.21504	0.10909	0.73246	0.0452*
H16	0.71862	−0.14548	−0.10142	0.0492*
H17	0.90225	−0.33603	−0.13232	0.0645*
H18	1.16340	−0.36590	−0.16526	0.0663*
H19	1.24041	−0.20984	−0.16395	0.0639*
H20	1.05705	−0.01834	−0.12595	0.0495*
H22	0.39907	0.22959	−0.11736	0.0667*
H23	0.38646	0.35207	−0.25697	0.0844*
H24	0.51177	0.48381	−0.27901	0.0757*
H25	0.66422	0.48465	−0.17083	0.0781*
H26	0.68364	0.36004	−0.03368	0.0618*
H1O	0.22282	0.86957	0.31621	0.0601*
H2O	0.19151	0.78537	0.29707	0.0601*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0631 (2)	0.0397 (2)	0.0533 (2)	−0.0185 (2)	−0.0129 (2)	0.0145 (2)
Cu1	0.0378 (2)	0.0381 (2)	0.0288 (2)	−0.0137 (2)	−0.0038 (1)	0.0081 (1)
S1	0.0439 (4)	0.0281 (3)	0.0275 (3)	−0.0113 (3)	0.0041 (3)	0.0020 (2)
S2	0.0398 (4)	0.0300 (3)	0.0285 (3)	−0.0075 (3)	−0.0020 (3)	0.0107 (3)
N1	0.0369 (12)	0.0270 (11)	0.0266 (10)	−0.0108 (10)	0.0011 (9)	0.0016 (8)
N2	0.0428 (13)	0.0266 (11)	0.0262 (10)	−0.0131 (10)	−0.0043 (9)	0.0043 (8)
N3	0.0330 (11)	0.0321 (12)	0.0272 (10)	−0.0096 (10)	−0.0013 (9)	0.0078 (9)
N4	0.0356 (12)	0.0284 (11)	0.0280 (11)	−0.0072 (10)	−0.0010 (9)	0.0072 (9)
C1	0.0285 (12)	0.0262 (12)	0.0266 (12)	−0.0073 (10)	−0.0060 (9)	0.0046 (9)
C2	0.0346 (13)	0.0298 (13)	0.0237 (11)	−0.0129 (11)	−0.0065 (10)	0.0062 (9)
C3	0.0377 (15)	0.0432 (16)	0.0379 (15)	−0.0174 (13)	−0.0118 (12)	0.0095 (12)
C4	0.061 (2)	0.055 (2)	0.0535 (19)	−0.0380 (18)	−0.0198 (16)	0.0120 (16)
C5	0.081 (3)	0.0372 (18)	0.070 (2)	−0.0297 (19)	−0.011 (2)	0.0072 (17)
C6	0.052 (2)	0.0324 (17)	0.082 (3)	−0.0068 (15)	−0.0023 (19)	0.0101 (17)
C7	0.0370 (15)	0.0352 (16)	0.0577 (19)	−0.0126 (13)	−0.0093 (14)	0.0148 (14)
C8	0.0323 (13)	0.0262 (13)	0.0332 (13)	−0.0089 (10)	−0.0093 (10)	0.0003 (10)
C9	0.066 (2)	0.0290 (15)	0.0455 (17)	−0.0106 (14)	−0.0203 (16)	0.0045 (12)
C10	0.079 (3)	0.0293 (16)	0.061 (2)	0.0008 (17)	−0.023 (2)	−0.0063 (15)
C11	0.063 (2)	0.0451 (19)	0.0463 (19)	−0.0051 (17)	−0.0126 (16)	−0.0163 (15)
C12	0.0524 (18)	0.0476 (18)	0.0328 (14)	−0.0154 (15)	−0.0138 (13)	0.0001 (13)
C13	0.0428 (16)	0.0317 (14)	0.0340 (14)	−0.0082 (12)	−0.0122 (12)	0.0029 (11)
C14	0.0277 (12)	0.0293 (13)	0.0276 (12)	−0.0115 (10)	−0.0064 (9)	0.0066 (10)
C15	0.0318 (13)	0.0350 (14)	0.0234 (11)	−0.0086 (11)	−0.0040 (10)	0.0025 (10)
C16	0.0389 (15)	0.0413 (16)	0.0409 (16)	−0.0144 (13)	−0.0095 (12)	−0.0046 (12)
C17	0.070 (2)	0.0355 (17)	0.0500 (19)	−0.0156 (16)	−0.0150 (17)	−0.0070 (14)
C18	0.057 (2)	0.0422 (19)	0.0456 (18)	0.0061 (16)	−0.0153 (16)	−0.0076 (14)
C19	0.0344 (16)	0.065 (2)	0.0468 (18)	−0.0018 (15)	−0.0127 (14)	−0.0062 (16)
C20	0.0356 (15)	0.0489 (18)	0.0384 (15)	−0.0164 (13)	−0.0087 (12)	−0.0002 (13)
C21	0.0342 (14)	0.0269 (13)	0.0326 (13)	−0.0080 (11)	−0.0036 (11)	0.0095 (10)
C22	0.060 (2)	0.061 (2)	0.066 (2)	−0.0357 (19)	−0.0326 (19)	0.0340 (19)
C23	0.078 (3)	0.085 (3)	0.071 (3)	−0.041 (3)	−0.044 (2)	0.044 (2)
C24	0.073 (3)	0.051 (2)	0.054 (2)	−0.0160 (19)	−0.0136 (19)	0.0303 (17)
C25	0.087 (3)	0.051 (2)	0.068 (2)	−0.042 (2)	−0.021 (2)	0.0278 (19)
C26	0.067 (2)	0.0484 (19)	0.0520 (19)	−0.0341 (18)	−0.0217 (17)	0.0159 (15)
O1	0.0479 (13)	0.0506 (14)	0.0404 (12)	−0.0115 (11)	−0.0050 (10)	0.0059 (10)

Geometric parameters (Å, º) top

Cu1—Br1	2.3387 (5)	C15—C20	1.380 (5)
Cu1—S1	2.2263 (8)	C16—C17	1.385 (5)
Cu1—S2	2.2129 (8)	C17—C18	1.387 (7)
S1—C1	1.709 (3)	C18—C19	1.354 (5)
S2—C14	1.705 (2)	C19—C20	1.394 (5)
O1—H1O	0.8300	C21—C22	1.367 (5)
O1—H2O	0.8000	C21—C26	1.381 (5)
N1—C1	1.336 (4)	C22—C23	1.387 (6)
N1—C2	1.424 (3)	C23—C24	1.368 (7)
N2—C1	1.343 (3)	C24—C25	1.367 (7)
N2—C8	1.418 (3)	C25—C26	1.382 (6)
N3—C15	1.428 (4)	C3—H3	0.9300
N3—C14	1.332 (3)	C4—H4	0.9300
N4—C14	1.340 (3)	C5—H5	0.9300
N4—C21	1.435 (3)	C6—H6	0.9300
N1—H1N	0.8600	C7—H7	0.9300
N2—H2N	0.8600	C9—H9	0.9300
N3—H3N	0.8600	C10—H10	0.9300
N4—H4N	0.8600	C11—H11	0.9300
C2—C3	1.377 (5)	C12—H12	0.9300
C2—C7	1.384 (5)	C13—H13	0.9300
C3—C4	1.385 (5)	C16—H16	0.9300
C4—C5	1.371 (6)	C17—H17	0.9300
C5—C6	1.379 (7)	C18—H18	0.9300
C6—C7	1.377 (5)	C19—H19	0.9300
C8—C13	1.387 (4)	C20—H20	0.9300
C8—C9	1.386 (4)	C22—H22	0.9300
C9—C10	1.387 (5)	C23—H23	0.9300
C10—C11	1.372 (5)	C24—H24	0.9300
C11—C12	1.377 (5)	C25—H25	0.9300
C12—C13	1.380 (5)	C26—H26	0.9300
C15—C16	1.383 (5)

Br1—Cu1—S1	125.03 (3)	C22—C21—C26	120.7 (3)
Br1—Cu1—S2	126.04 (3)	N4—C21—C26	119.9 (3)
S1—Cu1—S2	108.93 (3)	N4—C21—C22	119.4 (3)
Cu1—S1—C1	110.49 (9)	C21—C22—C23	119.5 (4)
Cu1—S2—C14	111.94 (9)	C22—C23—C24	120.3 (4)
H1O—O1—H2O	96.00	C23—C24—C25	119.7 (4)
C1—N1—C2	126.0 (2)	C24—C25—C26	120.9 (4)
C1—N2—C8	129.7 (2)	C21—C26—C25	118.9 (4)
C14—N3—C15	124.0 (2)	C2—C3—H3	120.00
C14—N4—C21	124.7 (2)	C4—C3—H3	120.00
C1—N1—H1N	117.00	C5—C4—H4	120.00
C2—N1—H1N	117.00	C3—C4—H4	120.00
C8—N2—H2N	115.00	C4—C5—H5	120.00
C1—N2—H2N	115.00	C6—C5—H5	120.00
C14—N3—H3N	118.00	C7—C6—H6	120.00
C15—N3—H3N	118.00	C5—C6—H6	120.00
C21—N4—H4N	118.00	C2—C7—H7	120.00
C14—N4—H4N	118.00	C6—C7—H7	120.00
S1—C1—N2	119.5 (2)	C10—C9—H9	120.00
N1—C1—N2	118.9 (2)	C8—C9—H9	120.00
S1—C1—N1	121.50 (19)	C11—C10—H10	120.00
C3—C2—C7	120.4 (3)	C9—C10—H10	120.00
N1—C2—C3	119.0 (3)	C10—C11—H11	120.00
N1—C2—C7	120.6 (3)	C12—C11—H11	120.00
C2—C3—C4	119.4 (4)	C11—C12—H12	120.00
C3—C4—C5	120.6 (4)	C13—C12—H12	120.00
C4—C5—C6	119.5 (4)	C12—C13—H13	120.00
C5—C6—C7	120.8 (4)	C8—C13—H13	120.00
C2—C7—C6	119.3 (4)	C15—C16—H16	120.00
N2—C8—C9	117.3 (2)	C17—C16—H16	120.00
C9—C8—C13	119.9 (3)	C18—C17—H17	120.00
N2—C8—C13	122.7 (2)	C16—C17—H17	120.00
C8—C9—C10	119.3 (3)	C17—C18—H18	120.00
C9—C10—C11	120.7 (3)	C19—C18—H18	120.00
C10—C11—C12	119.8 (3)	C20—C19—H19	120.00
C11—C12—C13	120.4 (3)	C18—C19—H19	120.00
C8—C13—C12	119.8 (3)	C15—C20—H20	120.00
S2—C14—N3	120.56 (19)	C19—C20—H20	120.00
S2—C14—N4	120.7 (2)	C23—C22—H22	120.00
N3—C14—N4	118.8 (2)	C21—C22—H22	120.00
N3—C15—C16	120.2 (3)	C22—C23—H23	120.00
C16—C15—C20	120.3 (3)	C24—C23—H23	120.00
N3—C15—C20	119.5 (3)	C25—C24—H24	120.00
C15—C16—C17	119.7 (4)	C23—C24—H24	120.00
C16—C17—C18	119.6 (4)	C24—C25—H25	120.00
C17—C18—C19	120.6 (3)	C26—C25—H25	120.00
C18—C19—C20	120.5 (4)	C21—C26—H26	121.00
C15—C20—C19	119.3 (3)	C25—C26—H26	121.00

Br1—Cu1—S1—C1	−7.29 (13)	C2—C3—C4—C5	−0.5 (6)
S2—Cu1—S1—C1	172.19 (12)	C3—C4—C5—C6	2.0 (7)
Br1—Cu1—S2—C14	−17.05 (13)	C4—C5—C6—C7	−1.1 (7)
S1—Cu1—S2—C14	163.48 (12)	C5—C6—C7—C2	−1.4 (6)
Cu1—S1—C1—N1	166.2 (2)	N2—C8—C9—C10	−177.1 (4)
Cu1—S1—C1—N2	−11.3 (3)	C13—C8—C9—C10	−1.0 (6)
Cu1—S2—C14—N3	176.2 (2)	N2—C8—C13—C12	177.9 (3)
Cu1—S2—C14—N4	−4.0 (3)	C9—C8—C13—C12	2.0 (6)
C2—N1—C1—S1	7.0 (4)	C8—C9—C10—C11	−0.4 (7)
C2—N1—C1—N2	−175.5 (3)	C9—C10—C11—C12	0.7 (7)
C1—N1—C2—C3	−130.1 (3)	C10—C11—C12—C13	0.3 (7)
C1—N1—C2—C7	53.2 (4)	C11—C12—C13—C8	−1.6 (6)
C8—N2—C1—S1	−169.9 (3)	N3—C15—C16—C17	−178.2 (3)
C8—N2—C1—N1	12.6 (5)	C20—C15—C16—C17	2.2 (5)
C1—N2—C8—C9	−150.7 (4)	N3—C15—C20—C19	179.5 (3)
C1—N2—C8—C13	33.2 (5)	C16—C15—C20—C19	−0.9 (5)
C15—N3—C14—S2	−1.0 (4)	C15—C16—C17—C18	−2.1 (5)
C15—N3—C14—N4	179.1 (3)	C16—C17—C18—C19	0.6 (6)
C14—N3—C15—C16	66.0 (4)	C17—C18—C19—C20	0.8 (6)
C14—N3—C15—C20	−114.4 (4)	C18—C19—C20—C15	−0.7 (5)
C21—N4—C14—S2	−172.0 (2)	N4—C21—C22—C23	179.8 (3)
C21—N4—C14—N3	7.9 (5)	C26—C21—C22—C23	−1.0 (5)
C14—N4—C21—C22	84.2 (4)	N4—C21—C26—C25	−178.9 (3)
C14—N4—C21—C26	−95.1 (4)	C22—C21—C26—C25	1.8 (5)
N1—C2—C3—C4	−178.8 (3)	C21—C22—C23—C24	−1.2 (6)
C7—C2—C3—C4	−2.0 (5)	C22—C23—C24—C25	2.5 (7)
N1—C2—C7—C6	179.6 (3)	C23—C24—C25—C26	−1.6 (7)
C3—C2—C7—C6	3.0 (5)	C24—C25—C26—C21	−0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.35	3.046 (4)	139
O1—H1O···S1ⁱⁱ	0.83	2.66	3.462 (3)	163
N2—H2N···Br1	0.86	2.59	3.435 (2)	169
N3—H3N···O1ⁱⁱⁱ	0.86	2.16	2.957 (3)	155
N4—H4N···Br1	0.86	2.72	3.573 (2)	170
C13—H13···N1	0.93	2.58	3.000 (4)	108
C13—H13···S2^iv	0.93	2.86	3.523 (3)	129
O1—H2O···CgDⁱⁱⁱ	0.80	2.78	3.306 (3)	125

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

Experimental details

Crystal data
Chemical formula	[CuBr(C₁₃H₁₂N₂S)₂]·H₂O
M_r	618.08
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.6195 (5), 12.1937 (6), 12.7969 (6)
α, β, γ (°)	89.345 (2), 73.154 (1), 69.225 (2)
V (Å³)	1336.20 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.50
Crystal size (mm)	0.28 × 0.23 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.509, 0.606
No. of measured, independent and observed [I > 2σ(I)] reflections	27804, 6568, 5426
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.122, 1.04
No. of reflections	6568
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −1.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Cu1—Br1	2.3387 (5)	Cu1—S2	2.2129 (8)
Cu1—S1	2.2263 (8)

Br1—Cu1—S1	125.03 (3)	S1—Cu1—S2	108.93 (3)
Br1—Cu1—S2	126.04 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.86	2.35	3.046 (4)	139
O1—H1O···S1ⁱⁱ	0.83	2.66	3.462 (3)	163
N2—H2N···Br1	0.86	2.59	3.435 (2)	169
N3—H3N···O1ⁱⁱⁱ	0.86	2.16	2.957 (3)	155
N4—H4N···Br1	0.86	2.72	3.573 (2)	170
C13—H13···N1	0.93	2.58	3.000 (4)	108
C13—H13···S2^iv	0.93	2.86	3.523 (3)	129
O1—H2O···CgDⁱⁱⁱ	0.80	2.78	3.306 (3)	125

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

Acknowledgements

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore and for technical support, respectively.

References

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