N-(2-Chloro­eth­yl)morpholine-4-carbox­amide

Ujam, O.T.; Asegbeloyin, J.N.; Nicholson, B.K.; Ukoha, P.O.; Ukwueze, N.N.

doi:10.1107/S1600536814005832

organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o463

doi:10.1107/S1600536814005832

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N-(2-Chloroethyl)morpholine-4-carboxamide

Oguejiofo T. Ujam,^a ^* Jonnie N. Asegbeloyin,^a Brian K. Nicholson,^b Pius O. Ukoha ^a and Nkechi N. Ukwueze ^a

^aDepartment of Pure and Industrial Chemistry, University of Nigeria, Nsukka, Enugu State, Nigeria, and ^bDepartment of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand
^*Correspondence e-mail: oguejiofo.ujam@unn.edu.ng

(Received 21 December 2013; accepted 16 March 2014; online 22 March 2014)

The title compound, C₇H₁₃ClN₂O₂, synthesized by the reaction of 2-chloroethyl isocyanate and morpholine, crystallizes with four molecules in the asymmetric unit, which have similar conformations and comprise two pairs each related by approximate non-crystallographic inversion centres. Two of them have a modest orientational disorder of the 2-chloroethyl fragments [occupancy ratio of 0.778 (4):0.222 (4)]. In the crystal, molecules are linked by N—H⋯O=C hydrogen bonds, forming three crystallographically different kinds of infinite hydrogen-bonded chains extending along [001].

CCDC reference: 991972

Related literature

For the solution-phase preparation of substituted morpholine derivatives, see: Lainton et al. (2003 ). For a related thiomorpholine analogue, see: Ujam et al. (2010 ); Henderson et al. (2006 ).

Experimental

Crystal data

C₇H₁₃ClN₂O₂
M_r = 192.64
Monoclinic, C c
a = 10.7393 (8) Å
b = 33.613 (3) Å
c = 9.9942 (7) Å
β = 95.704 (5)°
V = 3589.9 (5) Å³
Z = 16
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 99 K
0.30 × 0.10 × 0.10 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick 2003 ) T_min = 0.892, T_max = 0.962
39446 measured reflections
8451 independent reflections
5276 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.158
S = 1.04
8451 reflections
307 parameters
164 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.59 e Å⁻³
Absolute structure: Flack (1983 ), 4226 Friedel pairs
Absolute structure parameter: 0.38 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O6	0.85	2.03	2.831 (6)	157
N4—H4C⋯O4ⁱ	0.86	2.00	2.826 (6)	162
N6—H6C⋯O2ⁱⁱ	0.85	2.00	2.819 (6)	161
N8—H8C⋯O8ⁱⁱⁱ	0.82	2.05	2.809 (6)	153
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) $[x, -y+2, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 991972

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814005832/qk2064sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814005832/qk2064Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814005832/qk2064Isup3.mol

Supporting information file. DOI: 10.1107/S1600536814005832/qk2064Isup4.cml

checkCIF report

Comment top

The title compound, N-(2-chloroethyl) morpholine-4-carboxamide, was prepared as part of an ongoing project investigating the multifunctional alkylation of [Pt₂(µ-S)₂(PPh₃)₄] (Ujam et al., 2010). The X-ray structure determination established the molecular structure and atom connectivity of the title compound C₇H₁₃Cl₁N₂O₂ (Fig. 1). There are four independent molecules in the asymmetric unit which have the same overall conformation and comprise two pairs each related by approximate non-crystallographic inversion centres. Two of them have a modest orientation disorder of the 2-chloroethyl fragments. The molecules consist of a chair-shaped morpholine ring attached to a planar urea-type N₂CO unit. The 2-chloroethyl side chains are oriented approximately perpendicular to the N₂CO unit. In the crystal structure the molecules are linked by N—H···O═C hydrogen bonds (N···O = 2.809 (6) – 2.831 (6) Å) to form three crystallographically different kinds of infinite hydrogen bonded chains extending along [001] (Fig. 2), all with criss-cross patterns of molecule orientations when viewed along the chains (Fig. 3).

Experimental top

Morpholine [HN(CH₂CH₂)₂O, 200 mg, 0.002 mmol] was added to a solution of 2-chloroethyl isocyanate [ClCH₂CH₂NCO, 200 mg, 0.002 mmol] in diethyl ether (30 mL), immediately producing a white precipitate of the product. After stirring for 5 min the product was filtered and washed with ether (20 mL) and dried under vacuum to give ClCH₂CH₂NHC(O)N(CH₂CH₂)₂O. Crystals suitable for X-ray crystallographic analysis were obtained by vapour diffusion of diethyl ether into a dichloromethane solution.

Refinement top

Crystal data, data collection and structure refinement details are summarized in the crystallographic data Table. Diffraction images of the reciprocal space calculated from the recorded frame data were consistent with the crystallography reported and did reveal neither commensurate nor incommensurate superstructure reflections. All attempts to solve the structure in space group C2/c were unsuccessful, but it solved readily in Cc. The compound has four independent molecules in the asymmetric unit, comprising two pairs each related by an apparent inversion centre at x,y,z = 0.43, 0.63, 0.81 for the molecules 1 (Cl1, O1, O2, N1, N2, C1 through C7) and 2 (Cl2, N3, N4, O3, O4, C8 through C14), and at x,y,z = 0.42, 0.88, 0.31 for molecules molecules 3 (Cl3, O5, O6, N5, N6, C15 through C21) and 4 (Cl4, N7, N8, O7, O8, C22 through C28) . The two inversion centres were approximately related by 0 0.25 0.5 which is not a crystallographic relationship in C2/c, so the structure could not be converted to the centrosymmetric cell. Refinement was completed in the non-centrosymmetric space group Cc, and the crystal treated as a racemic twin. Unrestrained refinement led to a large spread in values for chemically equivalent bond parameters, and some unrealistic thermal ellipsoids, no doubt arising from instability associated with the pseudosymmetry. Hence the final refinement restrained the independent molecules to similar geometry using the SAME command of SHELXL, and EADP constraints were applied to equivalent atoms related by pseudosymmetry. Some residual electron density appeared to arise from partial disorder of the ethylene groups of two of the molecules (molecules 2 and 4) over two sites (0.78:0.22), so the C atoms of the minor component were included with fixed isotropic thermal parameters. Otherwise all non-hydrogen atoms were treated anisotropically. H atoms attached to carbon atoms were included in calculated positions [U_iso(H) = 1.2×U_equ(C)], but those attached to the amide N atoms were refined with DFIX constraints and U_iso(H) = 0.03 fixed.

Related literature top

For the solution-phase preparation of substituted morpholine derivatives, see: Lainton et al. (2003). For a related thiomorpholine analogue, see: Ujam et al. (2010); Henderson et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure and atom numbering of one of the four independent molecules of the title compound with displacement parameters drawn at the 40% probability level for non-H atoms.
	Fig. 2. Crystal structure of the compound showing the four different intermolecular N—H···O═C hydrogen bonds (dotted lines) within the three different hydrogen bond chains along [001]. C-bonded H atoms omitted for clarity.
	Fig. 3. Packing diagram of the title compound viewed along [001], the hydrogen bond chain direction. Symmetry equivalent molecules are colour coded and only Cl atoms were labeled. H atoms omitted for clarity.

N-(2-Chloroethyl)morpholine-4-carboxamide top

Crystal data top

C₇H₁₃ClN₂O₂	F(000) = 1632
M_r = 192.64	D_x = 1.426 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 10.7393 (8) Å	Cell parameters from 3770 reflections
b = 33.613 (3) Å	θ = 2–27°
c = 9.9942 (7) Å	µ = 0.39 mm⁻¹
β = 95.704 (5)°	T = 99 K
V = 3589.9 (5) Å³	Needle, colourless
Z = 16	0.30 × 0.10 × 0.10 mm

Data collection top

Siemens SMART CCD diffractometer	5276 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.082
ω scans	θ_max = 27.8°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick 2003)	h = −14→14
T_min = 0.892, T_max = 0.962	k = −43→44
39446 measured reflections	l = −13→13
8451 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.059	H-atom parameters constrained
wR(F²) = 0.158	w = 1/[σ²(F_o²) + (0.0582P)² + 2.927P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
8451 reflections	Δρ_max = 0.56 e Å⁻³
307 parameters	Δρ_min = −0.59 e Å⁻³
164 restraints	Absolute structure: Flack (1983), 4226 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.38 (17)

Crystal data top

C₇H₁₃ClN₂O₂	V = 3589.9 (5) Å³
M_r = 192.64	Z = 16
Monoclinic, Cc	Mo Kα radiation
a = 10.7393 (8) Å	µ = 0.39 mm⁻¹
b = 33.613 (3) Å	T = 99 K
c = 9.9942 (7) Å	0.30 × 0.10 × 0.10 mm
β = 95.704 (5)°

Data collection top

Siemens SMART CCD diffractometer	8451 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick 2003)	5276 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.962	R_int = 0.082
39446 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	H-atom parameters constrained
wR(F²) = 0.158	Δρ_max = 0.56 e Å⁻³
S = 1.04	Δρ_min = −0.59 e Å⁻³
8451 reflections	Absolute structure: Flack (1983), 4226 Friedel pairs
307 parameters	Absolute structure parameter: 0.38 (17)
164 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.

Refinement. Refined as a 2-component inversion twin (here a polar twin) with a component ratio of 0.38/0.62. The final refinement restrained the four independent molecules to similar geometry using the SAME command of SHELXL, and EADP constraints were applied to equivalent atom pairs related by pseudosymmetry. Some residual electron density appeared to arise from partial disorder of the ethylene groups of two of the molecules over two sites (0.78:0.22) so the C atoms of the minor component were included with fixed isotropic thermal parameters.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.1793 (6)	0.69065 (18)	0.5906 (7)	0.0257 (6)
H1A	0.2429	0.6694	0.5886	0.031*
H1B	0.1907	0.7095	0.5168	0.031*
C2	0.0503 (6)	0.67256 (17)	0.5692 (6)	0.0295 (6)
H2A	−0.0133	0.6940	0.5615	0.035*
H2B	0.0420	0.6572	0.4843	0.035*
C3	0.0387 (5)	0.66860 (16)	0.8026 (6)	0.0299 (6)
H3A	0.0211	0.6505	0.8767	0.036*
H3B	−0.0244	0.6901	0.7973	0.036*
C4	0.1672 (5)	0.68631 (15)	0.8331 (6)	0.0245 (6)
H4A	0.1701	0.7025	0.9161	0.029*
H4B	0.2300	0.6648	0.8478	0.029*
C5	0.2610 (4)	0.74577 (14)	0.7460 (5)	0.0216 (5)
C6	0.3614 (4)	0.80530 (13)	0.6609 (5)	0.0241 (6)
H6A	0.3323	0.8190	0.7397	0.029*
H6B	0.3423	0.8225	0.5810	0.029*
C7	0.4988 (4)	0.79800 (13)	0.6835 (6)	0.0317 (7)
H7A	0.5272	0.7829	0.6070	0.038*
H7B	0.5187	0.7822	0.7666	0.038*
N1	0.1972 (4)	0.71155 (12)	0.7195 (5)	0.0201 (5)
N2	0.2967 (4)	0.76644 (11)	0.6398 (4)	0.0308 (5)
H2C	0.2820 (5)	0.7572 (2)	0.5612 (18)	0.030*
O1	0.0284 (3)	0.64694 (11)	0.6785 (4)	0.0297 (4)
O2	0.2846 (3)	0.75889 (10)	0.8630 (4)	0.0292 (4)
Cl1	0.57778 (12)	0.84633 (4)	0.69906 (14)	0.0372 (2)
C8	0.6779 (6)	0.56216 (18)	1.0240 (7)	0.0257 (6)
H8A	0.6654	0.5439	1.0993	0.031*
H8B	0.6127	0.5830	1.0210	0.031*
C9	0.8058 (6)	0.58091 (17)	1.0459 (6)	0.0295 (6)
H9A	0.8108	0.5971	1.1291	0.035*
H9B	0.8695	0.5596	1.0592	0.035*
C10	0.8262 (5)	0.58296 (16)	0.8153 (6)	0.0299 (6)
H10A	0.8900	0.5616	0.8237	0.036*
H10B	0.8445	0.6005	0.7401	0.036*
C11	0.6986 (5)	0.56463 (15)	0.7835 (6)	0.0245 (6)
H11A	0.6352	0.5859	0.7661	0.029*
H11B	0.6979	0.5481	0.7016	0.029*
C12	0.5946 (4)	0.50722 (14)	0.8711 (5)	0.0216 (5)
C13	0.4970 (5)	0.44776 (15)	0.9575 (6)	0.0241 (6)	0.778 (4)
H13A	0.5150	0.4313	1.0393	0.029*
H13B	0.5310	0.4340	0.8815	0.029*
C14	0.3576 (5)	0.45371 (16)	0.9277 (7)	0.0317 (7)	0.778 (4)
H14A	0.3393	0.4683	0.8420	0.038*
H14B	0.3249	0.4694	1.0004	0.038*
N3	0.6675 (4)	0.54001 (12)	0.8967 (5)	0.0201 (5)
N4	0.5548 (4)	0.48731 (11)	0.9778 (4)	0.0308 (5)
H4C	0.5635 (4)	0.4978 (3)	1.0565 (18)	0.030*
O3	0.8346 (3)	0.60560 (10)	0.9370 (4)	0.0297 (4)
O4	0.5687 (3)	0.49474 (11)	0.7551 (4)	0.0292 (4)
Cl2	0.28368 (12)	0.40510 (4)	0.91603 (15)	0.0372 (2)
C15	0.1664 (6)	0.81124 (18)	0.0959 (7)	0.0268 (6)
H15A	0.1830	0.7940	0.0194	0.032*
H15B	0.2269	0.8335	0.1003	0.032*
C16	0.0353 (6)	0.82743 (18)	0.0734 (6)	0.0317 (6)
H16A	0.0273	0.8440	−0.0089	0.038*
H16B	−0.0244	0.8050	0.0592	0.038*
C17	0.0137 (5)	0.82715 (16)	0.3030 (6)	0.0283 (6)
H17A	−0.0465	0.8048	0.2915	0.034*
H17B	−0.0088	0.8437	0.3790	0.034*
C18	0.1445 (5)	0.81076 (16)	0.3359 (6)	0.0245 (6)
H18A	0.2035	0.8330	0.3580	0.029*
H18B	0.1461	0.7932	0.4156	0.029*
C19	0.2757 (4)	0.76025 (14)	0.2480 (5)	0.0220 (5)
C20	0.4416 (4)	0.71961 (12)	0.1643 (5)	0.0251 (6)
H20A	0.4928	0.7283	0.2470	0.030*
H20B	0.4929	0.7226	0.0879	0.030*
C21	0.4066 (4)	0.67709 (12)	0.1778 (6)	0.0270 (6)
H21A	0.3554	0.6680	0.0956	0.032*
H21B	0.3571	0.6736	0.2554	0.032*
N5	0.1841 (4)	0.78819 (12)	0.2215 (5)	0.0199 (4)
N6	0.3293 (4)	0.74516 (11)	0.1419 (4)	0.0298 (5)
H6C	0.2982 (8)	0.75040 (16)	0.0619 (18)	0.030*
O5	0.0041 (4)	0.85058 (10)	0.1835 (4)	0.0321 (4)
O6	0.3081 (3)	0.74858 (11)	0.3645 (4)	0.0281 (4)
Cl3	0.55040 (11)	0.64849 (4)	0.20263 (14)	0.03441 (18)
C22	0.6776 (6)	0.94101 (19)	0.5227 (7)	0.0268 (6)
H22A	0.6175	0.9186	0.5190	0.032*
H22B	0.6605	0.9586	0.5981	0.032*
C23	0.8101 (6)	0.92532 (18)	0.5449 (6)	0.0317 (6)
H23A	0.8690	0.9480	0.5557	0.038*
H23B	0.8199	0.9095	0.6289	0.038*
C24	0.8292 (5)	0.92350 (16)	0.3134 (6)	0.0283 (6)
H24A	0.8502	0.9064	0.2382	0.034*
H24B	0.8895	0.9459	0.3216	0.034*
C25	0.6977 (5)	0.93984 (16)	0.2819 (6)	0.0245 (6)
H25A	0.6942	0.9568	0.2006	0.029*
H25B	0.6380	0.9176	0.2637	0.029*
C26	0.5745 (5)	0.99248 (14)	0.3691 (5)	0.0220 (5)
C27	0.4059 (5)	1.03184 (15)	0.4504 (6)	0.0251 (6)	0.778 (4)
H27A	0.3535	1.0278	0.5254	0.030*
H27B	0.3574	1.0232	0.3660	0.030*
C28	0.4398 (5)	1.07526 (15)	0.4409 (6)	0.0270 (6)	0.778 (4)
H28A	0.4897	1.0796	0.3641	0.032*
H28B	0.4900	1.0839	0.5242	0.032*
N7	0.6630 (4)	0.96323 (12)	0.3958 (5)	0.0199 (4)
N8	0.5208 (4)	1.00824 (11)	0.4736 (4)	0.0298 (5)
H8C	0.5529 (8)	1.00457 (14)	0.5510 (18)	0.030*
O7	0.8412 (4)	0.90094 (10)	0.4351 (4)	0.0321 (4)
O8	0.5435 (3)	1.00387 (11)	0.2531 (4)	0.0281 (4)
Cl4	0.29550 (11)	1.10319 (3)	0.41732 (14)	0.03441 (18)
C13A	0.421 (2)	0.4712 (5)	0.954 (2)	0.030*	0.222 (4)
C14A	0.442 (2)	0.4253 (5)	0.939 (2)	0.030*	0.222 (4)
C27A	0.4955 (18)	1.0541 (6)	0.460 (2)	0.030*	0.222 (4)
C28A	0.3506 (17)	1.0513 (6)	0.427 (2)	0.030*	0.222 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0285 (14)	0.0265 (13)	0.0224 (14)	−0.0047 (11)	0.0047 (11)	−0.0045 (11)
C2	0.0326 (15)	0.0302 (14)	0.0251 (15)	−0.0090 (12)	0.0001 (11)	0.0000 (11)
C3	0.0297 (15)	0.0330 (13)	0.0280 (15)	−0.0047 (12)	0.0074 (12)	0.0043 (11)
C4	0.0281 (15)	0.0246 (12)	0.0203 (13)	−0.0047 (11)	0.0006 (11)	0.0037 (10)
C5	0.0194 (12)	0.0249 (12)	0.0204 (13)	0.0015 (10)	0.0019 (10)	0.0010 (10)
C6	0.0223 (14)	0.0251 (14)	0.0244 (14)	0.0013 (12)	0.0005 (11)	0.0010 (11)
C7	0.0235 (15)	0.0299 (14)	0.0420 (18)	0.0007 (12)	0.0056 (13)	0.0004 (13)
N1	0.0217 (12)	0.0223 (10)	0.0170 (11)	−0.0050 (9)	0.0049 (9)	−0.0001 (8)
N2	0.0403 (13)	0.0351 (12)	0.0168 (11)	−0.0182 (10)	0.0019 (9)	−0.0016 (9)
O1	0.0318 (11)	0.0288 (9)	0.0282 (11)	−0.0122 (8)	0.0021 (8)	0.0027 (8)
O2	0.0414 (11)	0.0290 (9)	0.0172 (9)	−0.0094 (8)	0.0037 (8)	−0.0030 (7)
Cl1	0.0332 (4)	0.0381 (4)	0.0398 (4)	−0.0168 (3)	0.0012 (3)	−0.0013 (3)
C8	0.0285 (14)	0.0265 (13)	0.0224 (14)	−0.0047 (11)	0.0047 (11)	−0.0045 (11)
C9	0.0326 (15)	0.0302 (14)	0.0251 (15)	−0.0090 (12)	0.0001 (11)	0.0000 (11)
C10	0.0297 (15)	0.0330 (13)	0.0280 (15)	−0.0047 (12)	0.0074 (12)	0.0043 (11)
C11	0.0281 (15)	0.0246 (12)	0.0203 (13)	−0.0047 (11)	0.0006 (11)	0.0037 (10)
C12	0.0194 (12)	0.0249 (12)	0.0204 (13)	0.0015 (10)	0.0019 (10)	0.0010 (10)
C13	0.0223 (14)	0.0251 (14)	0.0244 (14)	0.0013 (12)	0.0005 (11)	0.0010 (11)
C14	0.0235 (15)	0.0299 (14)	0.0420 (18)	0.0007 (12)	0.0056 (13)	0.0004 (13)
N3	0.0217 (12)	0.0223 (10)	0.0170 (11)	−0.0050 (9)	0.0049 (9)	−0.0001 (8)
N4	0.0403 (13)	0.0351 (12)	0.0168 (11)	−0.0182 (10)	0.0019 (9)	−0.0016 (9)
O3	0.0318 (11)	0.0288 (9)	0.0282 (11)	−0.0122 (8)	0.0021 (8)	0.0027 (8)
O4	0.0414 (11)	0.0290 (9)	0.0172 (9)	−0.0094 (8)	0.0037 (8)	−0.0030 (7)
Cl2	0.0332 (4)	0.0381 (4)	0.0398 (4)	−0.0168 (3)	0.0012 (3)	−0.0013 (3)
C15	0.0322 (16)	0.0287 (13)	0.0202 (14)	0.0083 (12)	0.0063 (11)	0.0035 (10)
C16	0.0370 (16)	0.0325 (14)	0.0244 (15)	0.0131 (12)	−0.0034 (12)	−0.0021 (11)
C17	0.0247 (14)	0.0296 (13)	0.0310 (15)	0.0063 (11)	0.0056 (11)	−0.0024 (11)
C18	0.0249 (14)	0.0261 (12)	0.0227 (14)	0.0040 (11)	0.0042 (11)	−0.0027 (10)
C19	0.0245 (13)	0.0234 (12)	0.0185 (13)	−0.0012 (10)	0.0043 (10)	−0.0012 (10)
C20	0.0209 (15)	0.0286 (13)	0.0271 (15)	−0.0016 (12)	0.0082 (11)	−0.0033 (11)
C21	0.0211 (15)	0.0274 (14)	0.0322 (16)	−0.0013 (12)	0.0005 (12)	−0.0019 (12)
N5	0.0233 (11)	0.0192 (9)	0.0175 (11)	0.0023 (8)	0.0028 (8)	0.0001 (8)
N6	0.0396 (13)	0.0344 (11)	0.0156 (11)	0.0191 (10)	0.0035 (9)	0.0012 (9)
O5	0.0360 (11)	0.0303 (9)	0.0293 (11)	0.0126 (8)	0.0001 (8)	−0.0031 (8)
O6	0.0343 (10)	0.0338 (9)	0.0163 (9)	0.0116 (8)	0.0031 (7)	0.0021 (7)
Cl3	0.0318 (4)	0.0353 (3)	0.0355 (4)	0.0150 (3)	0.0002 (3)	−0.0016 (3)
C22	0.0322 (16)	0.0287 (13)	0.0202 (14)	0.0083 (12)	0.0063 (11)	0.0035 (10)
C23	0.0370 (16)	0.0325 (14)	0.0244 (15)	0.0131 (12)	−0.0034 (12)	−0.0021 (11)
C24	0.0247 (14)	0.0296 (13)	0.0310 (15)	0.0063 (11)	0.0056 (11)	−0.0024 (11)
C25	0.0249 (14)	0.0261 (12)	0.0227 (14)	0.0040 (11)	0.0042 (11)	−0.0027 (10)
C26	0.0245 (13)	0.0234 (12)	0.0185 (13)	−0.0012 (10)	0.0043 (10)	−0.0012 (10)
C27	0.0209 (15)	0.0286 (13)	0.0271 (15)	−0.0016 (12)	0.0082 (11)	−0.0033 (11)
C28	0.0211 (15)	0.0274 (14)	0.0322 (16)	−0.0013 (12)	0.0005 (12)	−0.0019 (12)
N7	0.0233 (11)	0.0192 (9)	0.0175 (11)	0.0023 (8)	0.0028 (8)	0.0001 (8)
N8	0.0396 (13)	0.0344 (11)	0.0156 (11)	0.0191 (10)	0.0035 (9)	0.0012 (9)
O7	0.0360 (11)	0.0303 (9)	0.0293 (11)	0.0126 (8)	0.0001 (8)	−0.0031 (8)
O8	0.0343 (10)	0.0338 (9)	0.0163 (9)	0.0116 (8)	0.0031 (7)	0.0021 (7)
Cl4	0.0318 (4)	0.0353 (3)	0.0355 (4)	0.0150 (3)	0.0002 (3)	−0.0016 (3)

Geometric parameters (Å, º) top

C1—N1	1.463 (6)	C15—C16	1.506 (7)
C1—C2	1.509 (7)	C16—O5	1.415 (6)
C2—O1	1.429 (6)	C17—O5	1.426 (6)
C3—O1	1.433 (6)	C17—C18	1.514 (6)
C3—C4	1.506 (6)	C18—N5	1.470 (6)
C4—N1	1.478 (6)	C19—O6	1.244 (6)
C5—O2	1.252 (6)	C19—N6	1.354 (6)
C5—N1	1.352 (6)	C19—N5	1.367 (6)
C5—N2	1.355 (6)	C20—N6	1.480 (5)
C6—N2	1.485 (5)	C20—C21	1.487 (5)
C6—C7	1.491 (5)	C21—Cl3	1.815 (5)
C7—Cl1	1.832 (4)	C22—N7	1.467 (6)
C8—N3	1.469 (6)	C22—C23	1.513 (7)
C8—C9	1.507 (7)	C23—O7	1.435 (6)
C9—O3	1.427 (6)	C24—O7	1.428 (6)
C10—O3	1.430 (6)	C24—C25	1.519 (6)
C10—C11	1.507 (6)	C25—N7	1.462 (6)
C11—N3	1.466 (6)	C26—O8	1.235 (5)
C12—O4	1.239 (6)	C26—N8	1.351 (6)
C12—N3	1.362 (6)	C26—N7	1.375 (6)
C12—N4	1.362 (6)	C27—N8	1.466 (6)
C13—N4	1.473 (6)	C27—C28	1.509 (7)
C13—C14	1.510 (7)	C28—Cl4	1.807 (5)
C14—Cl2	1.815 (5)	C13A—C14A	1.568 (16)
C15—N5	1.471 (6)	C27A—C28A	1.561 (17)

N1—C1—C2	110.9 (5)	N5—C15—C16	110.9 (5)
O1—C2—C1	110.7 (5)	O5—C16—C15	111.9 (5)
O1—C3—C4	111.5 (5)	O5—C17—C18	111.8 (5)
N1—C4—C3	109.7 (5)	N5—C18—C17	110.7 (5)
O2—C5—N1	122.3 (5)	O6—C19—N6	120.9 (4)
O2—C5—N2	120.3 (4)	O6—C19—N5	121.8 (5)
N1—C5—N2	117.4 (5)	N6—C19—N5	117.3 (5)
N2—C6—C7	108.6 (4)	N6—C20—C21	111.2 (4)
C6—C7—Cl1	108.0 (3)	C20—C21—Cl3	107.6 (3)
C5—N1—C1	126.9 (5)	C19—N5—C18	117.6 (5)
C5—N1—C4	118.9 (5)	C19—N5—C15	123.8 (5)
C1—N1—C4	112.4 (4)	C18—N5—C15	111.6 (4)
C5—N2—C6	120.3 (4)	C19—N6—C20	120.1 (4)
C2—O1—C3	110.6 (4)	C16—O5—C17	110.2 (4)
N3—C8—C9	109.1 (5)	N7—C22—C23	108.8 (5)
O3—C9—C8	113.4 (5)	O7—C23—C22	112.0 (5)
O3—C10—C11	112.1 (5)	O7—C24—C25	111.8 (5)
N3—C11—C10	109.9 (5)	N7—C25—C24	109.7 (5)
O4—C12—N3	121.4 (5)	O8—C26—N8	120.5 (4)
O4—C12—N4	120.5 (4)	O8—C26—N7	121.4 (5)
N3—C12—N4	118.1 (5)	N8—C26—N7	118.0 (5)
N4—C13—C14	107.7 (4)	N8—C27—C28	109.2 (4)
C13—C14—Cl2	108.2 (4)	C27—C28—Cl4	107.5 (4)
C12—N3—C11	118.9 (5)	C26—N7—C25	117.3 (5)
C12—N3—C8	124.4 (5)	C26—N7—C22	123.0 (5)
C11—N3—C8	112.3 (4)	C25—N7—C22	112.7 (4)
C12—N4—C13	119.8 (4)	C26—N8—C27	120.5 (4)
C9—O3—C10	109.8 (4)	C24—O7—C23	109.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O6	0.85	2.03	2.831 (6)	157
N4—H4C···O4ⁱ	0.86	2.00	2.826 (6)	162
N6—H6C···O2ⁱⁱ	0.85	2.00	2.819 (6)	161
N8—H8C···O8ⁱⁱⁱ	0.82	2.05	2.809 (6)	153

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O6	0.85	2.03	2.831 (6)	156.9
N4—H4C···O4ⁱ	0.86	2.00	2.826 (6)	162.3
N6—H6C···O2ⁱⁱ	0.85	2.00	2.819 (6)	160.7
N8—H8C···O8ⁱⁱⁱ	0.82	2.05	2.809 (6)	152.6

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

Acknowledgements

We thank the Department of Pure and Industrial Chemistry, University of Nigeria, Nsukka, for some financial assistant and Dr Tania Groutso, University of Auckland, for the data collection.

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