Crystal structure of catena-poly[[cadmium(II)-di-μ2-bromido-μ2-l-proline-κ2O:O′] monohydrate]

Sathiskumar, S.; Balakrishnan, T.; Ramamurthi, K.; Thamotharan, S.

doi:10.1107/S2056989015001176

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Volume 71| Part 2| February 2015| Pages 217-219

doi:10.1107/S2056989015001176

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Crystal structure of catena-poly[[cadmium(II)-di-μ₂-bromido-μ₂-L-proline-κ²O:O′] monohydrate]

S. Sathiskumar,^a T. Balakrishnan,^a ^* K. Ramamurthi ^b and S. Thamotharan ^c ‡

^aCrystal Growth Laboratory, PG & Research Department of Physics, Periyar EVR College (Autonomous), Tiruchirappalli 620 023, India, ^bCrystal Growth and Thin Film Laboratory, Department of Physics and Nanotechnology, SRM University, Kattankulathur 603 203, India, and ^cDepartment of Bioinformatics, School of Chemical and Biotechnology, SASTRA University, Thanjavur 613 401, India
^*Correspondence e-mail: balacrystalgrowth@gmail.com

Edited by V. V. Chernyshev, Moscow State University, Russia (Received 29 December 2014; accepted 20 January 2015; online 24 January 2015)

In the title coordination polymer, {[CdBr₂(C₅H₉NO₂)]·H₂O}_n, the Cd^II ion is coordinated by four bromido ligands and two carboxylate oxygen atoms of two symmetry-related proline ligands, which exist in a zwitterionic form, in a distorted octahedral geometry. There is an intramolecular N—H⋯O hydrogen bond between the amino group and the carboxylate fragment. Each coordinating ligand bridges two Cd^II atoms, thus forming polymeric chains running along the c-axis direction. The water molecules of crystallization serve as donors for the weak intermolecular O—H⋯O and O—H⋯Br hydrogen bonds that link adjacent polymeric chains, thus forming a three-dimensional structure. N—H⋯O and N—H⋯Br hydrogen bonds also occur.

Keywords: crystal structure; L-proline cadmium bromide; cadmium coordination polymer; N/O—H⋯Br/O hydrogen bonds; distorted octahedral geometry..

CCDC reference: 1044327

1. Chemical context

The characterization of second-order non-linear optical (NLO) materials is important because of their potential applications such as frequency shifting, optical modulation, optical switching, telecommunication and signal processing. It is known that the chiral amino acids and their complexes are potential materials for NLO applications (Eimerl et al., 1989 ; Pal et al., 2004 ; Srinivasan et al., 2006 ). This study is a part of an ongoing investigation of the crystal and molecular structures of a series of amino acid–metal complexes (Sathiskumar et al., 2015 ; Balakrishnan et al., 2013 ).

2. Structural commentary

The asymmetric unit of the title complex (I) (Fig. 1) contains one Cd^II ion, one proline and two bromido ligands, and one water molecule of crystallization. The title complex has a very similar structure to that of the chloride analogue (Yukawa et al., 1983 ) and L-proline manganese dichloride monohydrate (Rzączyńska et al., 1997 ; Lamberts & Englert, 2012 ). In (I), proline exists in a zwitterionic form, as evident from the bond lengths involving the carboxylate atoms and the protonation of the ring N atom of the pyrrolidine fragment. The Cd^II ion is coordinated by four bromido ligands [Cd—Br = 2.7236 (13)–2.7737 (12) Å] and two carboxylate oxygen atoms [Cd—O = 2.312 (8) and 2.318 (8) Å] of two proline ligands in a slightly distorted octahedral geometry. The title complex is extended as a polymeric chain which runs parallel to the c axis. Within one chain, adjacent Cd^II ions are separated by 3.727 (1) Å. The closest Cd⋯Cd distance between neighbouring polymeric chains is 8.579 (2) Å. The five endocyclic torsion angles of the pyrrolidine ring of the proline residue are N1—C2—C3—C4 = 31.8 (13)°, C2—C3—C4—C5 = −39.1 (15)°, C3—C4—C5—N1 = 29.9 (14)°, C2—N1—C5—C4 = −9.7 (12)° and C5—N1—C2—C3 = −13.1 (11)°. The pyrrolidine ring exhibits twisted conformation on the C3—C4 bond with a pseudo-rotation angle Δ = 249.3 (12)° and a maximum torsion angle φ_m = 38.5 (8)° (Rao et al., 1981 ).

Figure 1
A portion of the crystal structure of the title complex, showing the atomic labeling. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (a) $[{1\over 2}]$ − x, −y, z − $[{1\over 2}]$ ; (b) $[{1\over 2}]$ − x, −y, z + $[{1\over 2}]$ .]

In (I), as observed in the chloride analogue (Yukawa et al., 1983), there is an intramolecular N1—H1A⋯O2 hydrogen bond between the amino group and the carboxylate fragment.

3. Supramolecular features

The crystal structure of (I), is stabilized by intermolecular N—H⋯O, N—H⋯Br, O—H⋯O and O—H⋯Br hydrogen bonds (Table 1, Figs. 2 and 3). The water molecules serve as donors for the weak O—H⋯O and O—H⋯Br hydrogen bonds (Table 1) which link adjacent polymeric chains (Fig. 3), thus forming a three-dimensional structure.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.89	2.16	2.626 (12)	112
O1W—H2W⋯O1	0.84 (17)	2.6 (2)	3.175 (19)	132
O1W—H2W⋯Br2	0.84 (17)	2.8 (3)	3.311 (19)	123
N1—H1A⋯O1Wⁱ	0.89	2.05	2.90 (2)	159
N1—H1B⋯Br1ⁱⁱ	0.89	2.69	3.416 (11)	140
O1W—H1W⋯Br2ⁱⁱⁱ	0.88 (16)	2.7 (3)	3.197 (19)	116
Symmetry codes: (i) x, y, z-1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 2
The crystal packing of (I)

viewed along the a axis. Dashed lines denote intermolecular hydrogen bonds. C-bound H atoms have been omitted for clarity.

Figure 3
A portion of the crystal packing viewed along the a axis and showing hydrogen bonds (dashed lines) between two neighbouring polymeric chains.

4. Database survey

A search in the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014 ) for the structures with metal ions coordinated by one of the carboxylate oxygen atoms of the proline moiety yielded 44 hits. Of these, two structures contain a cadmium metal ion, viz. catena-[dichlorido-(4-hydroxy-L-proline)cadmium] (refcode BOHVID; Yukawa et al., 1982 ) and catena-[bis(μ²-chlorido)(μ₂-L-proline)cadmium monohydrate] (refcode BUXBUR; Yukawa et al., 1983). The latter structure is isotypic with the title complex. Another compound, catena-[bis(μ₂-chlorido)(μ₂-L-prolinato-κ²-O,O′)manganese(II) monohydrate], has been structurally determined three times and has similar cell parameters and the same space group as the title compound (refcode ROJQEM: Rzączyńska et al., 1997; refcode ROJEQM01: Tilborg et al., 2010 ; refcode ROJQEM02: Lamberts & Englert, 2012).

5. Synthesis and crystallization

To prepare the title compound, L-proline (Loba) and cadmium bromide tetrahydrate (Loba) in an equimolar ratio were dissolved in double-distilled water. The obtained solution of the homogeneous mixture was evaporated at room temperature to afford the white crystalline title compound, which was then recrystallized by slow evaporation from an aqueous solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. As the title compound is isotypic with its chlorido analogue (Yukawa et al., 1983), the atomic coordinates of the latter were used as starting values in the initial cycles of the refinement. The positions of water hydrogen atoms were calculated by method of Nardelli (1999 ). Further, the O—H and H1W⋯H2W distances of the water molecules were restrained to 0.85 (2) and 1.38 (2) Å, respectively, using the DFIX option and included in the structure-factor calculations with U_iso(H1W/H2W) = 1.1U_eq(O1W). The remaining hydrogen atoms were placed in geometrically idealized positions (C—H = 0.97–0.98 Å and N—H = 0.89 Å) with U_iso(H) = 1.2U_eq(C/N) and were constrained to ride on their parent atoms. Reflections 110 and 020 were partially obscured by the beam stop and were omitted.

Table 2
Experimental details

Crystal data
Chemical formula	[CdBr₂(C₅H₉NO₂)]·H₂O
M_r	405.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	10.1891 (8), 13.4961 (11), 7.4491 (5)
V (Å³)	1024.35 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	9.90
Crystal size (mm)	0.35 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.129, 0.155
No. of measured, independent and observed [I > 2σ(I)] reflections	8264, 2481, 1964
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.089, 1.06
No. of reflections	2481
No. of parameters	115
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.02, −1.07
Absolute structure	Flack x determined using 705 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.035 (15)
Computer programs: APEX2, SAINT and XPREP (Bruker, 2008), SHELXL2014/6 (Sheldrick, 2015 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1044327

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015001176/cv5483sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015001176/cv5483Isup2.hkl

checkCIF report

Chemical context top

The characterization of second-order non-linear optical (NLO) materials is important because of their potential applications such as frequency shifting, optical modulation, optical switching, telecommunication and signal processing. It is known that the chiral amino acids and their complexes are potential materials for NLO applications (Eimerl et al., 1989; Pal et al., 2004; Srinivasan et al., 2006). This study is a part of an ongoing investigation of the crystal and molecular structures of a series of amino acid–metal complexes (Sathiskumar et al., 2015; Balakrishnan et al., 2013).

Structural commentary top

The asymmetric unit of the title complex (I) (Fig. 1) contains one Cd^II ion, one proline and two bromido ligands, and one water molecule of crystallization. The title complex has a very similar structure to that of the chloride analogue (Yukawa et al., 1983) and L-proline manganese dichloride monohydrate (Rzączyńska et al., 1997; Lamberts & Englert, 2012). In (I), proline exists in a zwitterionic form, as evident from the bond lengths involving the carboxylate atoms and the protonation of the ring N atom of the pyrrolidine fragment. The Cd^II ion is coordinated by four bromido ligands [Cd—Br = 2.7236 (13)–2.7737 (12) Å] and two carboxylate oxygen atoms [Cd—O = 2.312 (8) and 2.318 (8) Å] of the proline ligand in a slightly distorted octahedral geometry. The title complex is extended as a polymeric chain which runs parallel to the c axis. Within one chain, adjacent Cd^II ions are separated by 3.727 (1) Å. The closest Cd···Cd distance between neighbouring polymeric chains is is 8.579 (2) Å. The five endocyclic torsion angles of the pyrrolidine ring of the proline residue are N1—C2—C3—C4 = 31.8 (13)°, C2—C3—C4—C5 = -39.1 (15)°, C3—C4—C5—N1 = 29.9 (14)°, C2—N1—C5—C4 = -9.7 (12)° and C5—N1—C2—C3 = -13.1 (11)°. The pyrrolidine ring exhibits twisted conformation on the C3—C4 bond with a pseudo-rotation angle Δ = 249.3 (12)° and a maximum torsion angle ϕ_m = 38.5 (8)° (Rao et al., 1981).

In (I), as observed in the chloride analogue (Yukawa et al., 1983), there is an intramolecular N1—H1A···O2 hydrogen bond between the amino group and the carboxylate fragment.

Supramolecular features top

The crystal structure of (I), is stabilized by intermolecular N—H···O, N—H···Br, O—H···O and O—H···Br hydrogen bonds (Table 1, Figs. 2 and 3). The water molecules serve as donors for the weak O—H···O and O—H···Br hydrogen bonds (Table 1) which link adjacent polymeric chains (Fig. 3), thus forming a three-dimensional structure.

Database survey top

A search in the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014) for the structures with metal ions coordinated by one of the carboxylate oxygen atoms of the proline moiety yielded 44 hits. Of these, two structures contain a cadmium metal ion, viz. catena[dichloro-(4-hydroxy-L-proline)cadmium(II)] (refcode BOHVID; Yukawa et al., 1982) and catena-[bis(µ²-chloro)(µ₂-L-proline)cadmium(II) monohydrate] (refcode BUXBUR; Yukawa et al., 1983). The latter structure is isotypic with the title complex. The cell parameters and space groups of three other structures are similar to those of the title complex. They are catena-[bis(µ₂-chloro)(µ₂-L-prolinato-κ²-O,O')manganese(II) monohydrate] (refcode ROJQEM; Rzączyńska et al., 1997), catena-[(µ₂-L-prolinato)bis(µ₂-chloro)manganese(II) monohydrate] (refcode ROJEQM01; Tilborg et al., 2010) and catena-[bis(µ₂-chloro)(µ₂-L-prolinato)manganese(II) monohydrate] (refcode ROJQEM02; Lamberts & Englert, 2012).

Synthesis and crystallization top

Refinement top

As the title compound is isotypic with its chlorido analogue (Yukawa et al., 1983), the atomic coordinates of the latter were used as starting values in the initial cycles of the refinement. The positions of water hydrogen atoms were calculated by method of Nardelli (1999). Further, the O—H and H1W···H2W distances of the water molecules were restrained to 0.85 (2) and 1.38 (2) Å, respectively, using the DFIX option and included in the structure-factor calculations with U_iso(H1W/H2W) = 1.1U_eq(O1W). The remaining hydrogen atoms were placed in geometrically idealized positions (C—H = 0.97–0.98 Å and N—H = 0.89 Å) with U_iso(H) = 1.2U_eq(C/N) and were constrained to ride on their parent atoms. Reflections 110 and 020 were partially obscured by the beam stop and were omitted.

Related literature top

For related literature, see: Balakrishnan et al. (2013); Eimerl et al. (1989); Groom & Allen (2014); Lamberts & Englert (2012); Nardelli (1999); Pal et al. (2004); Parsons et al. (2013); Rao et al. (1981); Rzączyńska et al. (1997); Sathiskumar et al. (2015); Srinivasan et al. (2006); Tilborg et al. (2010); Yukawa et al. (1982, 1983).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: atomic coordinates of chlorido analogue (Yukawa et al., 1983) used as starting values in the initial cycles of the refinement; program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Figures top

	Fig. 1. A portion of the crystal structure of the title complex, showing the atomic labeling. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (a) 1/2 - x, -y, z - 1/2; (b) 1/2 - x, -y, z + 1/2.]
	Fig. 2. The crystal packing of (I) viewed along the a axis. Dashed lines denote intermolecular hydrogen bonds. C-bound H atoms have been omitted for clarity.
	Fig. 3. A portion of the crystal packing viewed along the a axis and showing hydrogen bonds (dashed lines) between two neighbouring polymeric chains.

catena-Poly[[cadmium(II)-di-µ₂-bromido-µ₂-L-proline-κ²O:O'] monohydrate] top

Crystal data top

[CdBr₂(C₅H₉NO₂)]·H₂O	D_x = 2.629 Mg m⁻³
M_r = 405.37	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 4066 reflections
a = 10.1891 (8) Å	θ = 5.0–55.2°
b = 13.4961 (11) Å	µ = 9.90 mm⁻¹
c = 7.4491 (5) Å	T = 296 K
V = 1024.35 (13) Å³	Block, colourless
Z = 4	0.35 × 0.30 × 0.30 mm
F(000) = 760

Data collection top

Bruker SMART CCD area detector diffractometer	1964 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
ω and ϕ scan	θ_max = 28.2°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
T_min = 0.129, T_max = 0.155	k = −17→14
8264 measured reflections	l = −9→6
2481 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0243P)² + 1.4185P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 1.02 e Å⁻³
2481 reflections	Δρ_min = −1.07 e Å⁻³
115 parameters	Absolute structure: Flack x determined using 705 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
3 restraints	Absolute structure parameter: 0.035 (15)

Crystal data top

[CdBr₂(C₅H₉NO₂)]·H₂O	V = 1024.35 (13) Å³
M_r = 405.37	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.1891 (8) Å	µ = 9.90 mm⁻¹
b = 13.4961 (11) Å	T = 296 K
c = 7.4491 (5) Å	0.35 × 0.30 × 0.30 mm

Data collection top

Bruker SMART CCD area detector diffractometer	2481 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1964 reflections with I > 2σ(I)
T_min = 0.129, T_max = 0.155	R_int = 0.068
8264 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.089	Δρ_max = 1.02 e Å⁻³
S = 1.06	Δρ_min = −1.07 e Å⁻³
2481 reflections	Absolute structure: Flack x determined using 705 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
115 parameters	Absolute structure parameter: 0.035 (15)
3 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.24415 (7)	0.00192 (7)	0.31349 (9)	0.0425 (2)
Br1	0.44442 (8)	0.03071 (8)	0.06673 (14)	0.0450 (3)
Br2	0.37743 (10)	0.11262 (9)	0.56256 (15)	0.0537 (3)
O1	0.1309 (8)	0.1397 (6)	0.2136 (9)	0.057 (2)
O2	0.1420 (7)	0.1362 (6)	−0.0865 (9)	0.056 (2)
N1	−0.0870 (10)	0.2205 (8)	−0.1393 (11)	0.062 (3)
H1A	−0.0168	0.2171	−0.2100	0.075*
H1B	−0.1202	0.2813	−0.1471	0.075*
C1	0.0861 (9)	0.1560 (7)	0.0564 (15)	0.039 (2)
C2	−0.0488 (10)	0.1988 (8)	0.0510 (15)	0.053 (3)
H2	−0.0524	0.2596	0.1229	0.064*
C3	−0.1523 (12)	0.1260 (13)	0.115 (2)	0.084 (5)
H3A	−0.1172	0.0826	0.2066	0.100*
H3B	−0.2279	0.1607	0.1627	0.100*
C4	−0.1878 (13)	0.0697 (13)	−0.047 (2)	0.094 (5)
H4A	−0.2733	0.0392	−0.0326	0.113*
H4B	−0.1236	0.0181	−0.0701	0.113*
C5	−0.1899 (14)	0.1441 (12)	−0.200 (2)	0.086 (5)
H5A	−0.2758	0.1743	−0.2126	0.103*
H5B	−0.1651	0.1134	−0.3127	0.103*
O1W	0.111 (2)	0.2521 (17)	0.587 (2)	0.183 (8)
H1W	0.11 (3)	0.296 (11)	0.50 (2)	0.201*
H2W	0.13 (3)	0.197 (8)	0.54 (3)	0.201*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0453 (4)	0.0579 (4)	0.0243 (3)	0.0069 (4)	−0.0005 (2)	0.0045 (3)
Br1	0.0347 (4)	0.0679 (7)	0.0323 (4)	0.0033 (5)	−0.0007 (4)	−0.0001 (5)
Br2	0.0597 (6)	0.0687 (7)	0.0327 (5)	−0.0117 (6)	0.0013 (5)	−0.0056 (6)
O1	0.074 (5)	0.066 (5)	0.032 (4)	0.025 (4)	−0.011 (3)	−0.005 (4)
O2	0.059 (5)	0.068 (5)	0.043 (4)	0.016 (4)	0.005 (4)	0.007 (4)
N1	0.063 (6)	0.066 (7)	0.058 (6)	0.037 (6)	−0.015 (5)	−0.001 (5)
C1	0.040 (5)	0.039 (5)	0.039 (5)	0.005 (4)	−0.002 (5)	−0.003 (5)
C2	0.053 (6)	0.060 (7)	0.046 (5)	0.024 (6)	−0.009 (6)	−0.010 (6)
C3	0.043 (7)	0.113 (13)	0.095 (10)	0.005 (8)	0.018 (6)	0.008 (10)
C4	0.042 (6)	0.110 (12)	0.130 (13)	−0.008 (8)	0.006 (9)	−0.021 (13)
C5	0.075 (9)	0.090 (11)	0.091 (10)	0.040 (9)	−0.024 (8)	−0.037 (9)
O1W	0.178 (16)	0.22 (2)	0.153 (13)	0.061 (18)	0.007 (14)	0.061 (17)

Geometric parameters (Å, º) top

Cd1—O1	2.312 (8)	N1—H1B	0.8900
Cd1—O2ⁱ	2.318 (8)	C1—C2	1.491 (13)
Cd1—Br2ⁱⁱ	2.7236 (13)	C2—C3	1.517 (19)
Cd1—Br1ⁱ	2.7285 (11)	C2—H2	0.9800
Cd1—Br2	2.7421 (13)	C3—C4	1.47 (2)
Cd1—Br1	2.7737 (12)	C3—H3A	0.9700
Br1—Cd1ⁱⁱ	2.7285 (11)	C3—H3B	0.9700
Br2—Cd1ⁱ	2.7236 (13)	C4—C5	1.52 (2)
O1—C1	1.276 (12)	C4—H4A	0.9700
O2—C1	1.237 (12)	C4—H4B	0.9700
O2—Cd1ⁱⁱ	2.318 (8)	C5—H5A	0.9700
N1—C2	1.499 (13)	C5—H5B	0.9700
N1—C5	1.537 (17)	O1W—H1W	0.87 (3)
N1—H1A	0.8900	O1W—H2W	0.87 (3)

O1—Cd1—O2ⁱ	179.9 (3)	O1—C1—C2	114.9 (9)
O1—Cd1—Br2ⁱⁱ	90.50 (19)	C1—C2—N1	109.9 (9)
O2ⁱ—Cd1—Br2ⁱⁱ	89.53 (19)	C1—C2—C3	112.4 (10)
O1—Cd1—Br1ⁱ	90.0 (2)	N1—C2—C3	103.9 (10)
O2ⁱ—Cd1—Br1ⁱ	90.03 (19)	C1—C2—H2	110.1
Br2ⁱⁱ—Cd1—Br1ⁱ	93.59 (4)	N1—C2—H2	110.1
O1—Cd1—Br2	91.52 (19)	C3—C2—H2	110.1
O2ⁱ—Cd1—Br2	88.44 (19)	C4—C3—C2	104.5 (11)
Br2ⁱⁱ—Cd1—Br2	177.29 (3)	C4—C3—H3A	110.9
Br1ⁱ—Cd1—Br2	88.22 (3)	C2—C3—H3A	110.9
O1—Cd1—Br1	92.4 (2)	C4—C3—H3B	110.9
O2ⁱ—Cd1—Br1	87.56 (19)	C2—C3—H3B	110.9
Br2ⁱⁱ—Cd1—Br1	87.67 (4)	H3A—C3—H3B	108.9
Br1ⁱ—Cd1—Br1	177.27 (4)	C3—C4—C5	106.0 (12)
Br2—Cd1—Br1	90.44 (4)	C3—C4—H4A	110.5
Cd1ⁱⁱ—Br1—Cd1	85.27 (3)	C5—C4—H4A	110.5
Cd1ⁱ—Br2—Cd1	85.98 (3)	C3—C4—H4B	110.5
C1—O1—Cd1	127.7 (6)	C5—C4—H4B	110.5
C1—O2—Cd1ⁱⁱ	132.9 (7)	H4A—C4—H4B	108.7
C2—N1—C5	108.9 (10)	C4—C5—N1	102.3 (10)
C2—N1—H1A	109.9	C4—C5—H5A	111.3
C5—N1—H1A	109.9	N1—C5—H5A	111.3
C2—N1—H1B	109.9	C4—C5—H5B	111.3
C5—N1—H1B	109.9	N1—C5—H5B	111.3
H1A—N1—H1B	108.3	H5A—C5—H5B	109.2
O2—C1—O1	126.0 (8)	H1W—O1W—H2W	106 (4)
O2—C1—C2	119.0 (10)

Cd1ⁱⁱ—O2—C1—O1	44.5 (15)	C5—N1—C2—C1	107.4 (11)
Cd1ⁱⁱ—O2—C1—C2	−132.7 (9)	C5—N1—C2—C3	−13.1 (11)
Cd1—O1—C1—O2	−40.4 (15)	C1—C2—C3—C4	−87.0 (14)
Cd1—O1—C1—C2	136.8 (8)	N1—C2—C3—C4	31.8 (13)
O2—C1—C2—N1	−6.1 (15)	C2—C3—C4—C5	−39.1 (15)
O1—C1—C2—N1	176.4 (9)	C3—C4—C5—N1	29.9 (14)
O2—C1—C2—C3	109.1 (12)	C2—N1—C5—C4	−9.7 (12)
O1—C1—C2—C3	−68.3 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	2.16	2.626 (12)	112
O1W—H2W···O1	0.84 (17)	2.6 (2)	3.175 (19)	132
O1W—H2W···Br2	0.84 (17)	2.8 (3)	3.311 (19)	123
N1—H1A···O1Wⁱⁱⁱ	0.89	2.05	2.90 (2)	159
N1—H1B···Br1^iv	0.89	2.69	3.416 (11)	140
O1W—H1W···Br2^v	0.88 (16)	2.7 (3)	3.197 (19)	116

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.89	2.16	2.626 (12)	112.1
O1W—H2W···O1	0.84 (17)	2.6 (2)	3.175 (19)	132
O1W—H2W···Br2	0.84 (17)	2.8 (3)	3.311 (19)	123
N1—H1A···O1Wⁱ	0.89	2.05	2.90 (2)	159
N1—H1B···Br1ⁱⁱ	0.89	2.69	3.416 (11)	140
O1W—H1W···Br2ⁱⁱⁱ	0.88 (16)	2.7 (3)	3.197 (19)	116

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

Experimental details

Crystal data
Chemical formula	[CdBr₂(C₅H₉NO₂)]·H₂O
M_r	405.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	10.1891 (8), 13.4961 (11), 7.4491 (5)
V (Å³)	1024.35 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.90
Crystal size (mm)	0.35 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.129, 0.155
No. of measured, independent and observed [I > 2σ(I)] reflections	8264, 2481, 1964
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.089, 1.06
No. of reflections	2481
No. of parameters	115
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.02, −1.07
Absolute structure	Flack x determined using 705 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Absolute structure parameter	0.035 (15)

Computer programs: APEX2 (Bruker, 2008), APEX2 and SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), atomic coordinates of chlorido analogue (Yukawa et al., 1983) used as starting values in the initial cycles of the refinement, SHELXL2014/6 (Sheldrick, 2015), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).

Footnotes

‡Additional correspondence author, e-mail: thamu@scbt.sastra.edu.

Acknowledgements

TB and SS acknowledge the University Grants Commission (UGC), New Delhi, India, for providing financial support [project ref. No. 41–956/2012(SR)]. ST is very grateful to the management of SASTRA University for infrastructural and financial support (Professor TRR grant).

References

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Volume 71| Part 2| February 2015| Pages 217-219

doi:10.1107/S2056989015001176

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