catena-Poly[[diaqua­bis­{μ2-3,5-bis­[(pyridin-4-yl)methyl­amino]­benzoato}nickel] monohydrate]

Kuai, H.-W.; Cheng, X.-C.

doi:10.1107/S1600536811038633

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Pages m1458-m1459

https://doi.org/10.1107/S1600536811038633

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catena-Poly[[diaquabis{μ₂-3,5-bis[(pyridin-4-yl)methylamino]benzoato}nickel] monohydrate]

Hai-Wei Kuai ^a ^* and Xiao-Chun Cheng ^a

^aFaculty of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaian 223003, People's Republic of China
^*Correspondence e-mail: hyitshy@126.com

(Received 12 September 2011; accepted 20 September 2011; online 30 September 2011)

In the title coordination polymer, {[Ni(C₁₉H₁₇N₄O₂)₂(H₂O)₂]·H₂O}_n, the Ni²⁺ cation is located on an inversion center and coordinated by two carboxylate O atoms from two different 3,5-bis(pyridin-4-ylmethylamino)benzoate anions, two O atoms from two coordinated water molecules and two N atoms from two different 3,5-bis(pyridin-4-ylmethylamino)benzoate anions, displaying a slightly distorted NiN₂O₄ octahedral geometry. Each 3,5-bis(pyridin-4-ylmethylamino)benzoate anion acts as a μ₂-bridge, linking different nickel ions into a chain along [010]. In the crystal, adjacent chains are further linked through N—H⋯O, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds into a three-dimensional network. The coordinated water molecules and a disordered water molecule of hydration with 0.50 site occupancy play an important role in the formation of these hydrogen-bonding interactions.

Related literature

For background to metal-organic hybrid materials, see: Bradshaw et al. (2005 ); Das & Bharadwaj (2009 ); Hua et al. (2010 ). For the use of N-, or O- multidentate donor ligands as building blocks in the construction of infinite frameworks, see: Peng et al. (2010 ). For related structures, see: Chen et al. (2009 ); Kuai et al. (2011 ).

Experimental

Crystal data

[Ni(C₁₉H₁₇N₄O₂)₂(H₂O)₂]·H₂O
M_r = 779.49
Monoclinic, P 2₁ /c
a = 10.7786 (10) Å
b = 9.3152 (9) Å
c = 18.1211 (17) Å
β = 92.324 (1)°
V = 1817.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.880, T_max = 0.900
11129 measured reflections
4300 independent reflections
2688 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.094
S = 0.90
4300 reflections
250 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H10⋯O3ⁱ	0.92	2.13	3.023 (2)	163
O3—H18⋯O2	0.86	1.77	2.627 (2)	169
O4—H21⋯O2ⁱⁱ	0.90	2.09	2.701 (5)	125
O4—H20⋯O2ⁱⁱⁱ	1.06	1.72	2.690 (5)	150
O3—H19⋯N31^iv	0.97	1.87	2.787 (3)	156
C2—H1⋯O4^v	0.93	2.58	3.505 (6)	172
C37—H16⋯O4^v	0.97	2.47	3.440 (8)	176
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z; (iv) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S1600536811038633/pv2448sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038633/pv2448Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811038633/pv2448Isup4.cdx

checkCIF report

Comment top

During the past few decades, growing interests have been focused on the rapidly expanding field of crystal engineering of metal-organic frameworks (MOFs) due to their intriguing architectures as well as their tremendous potential applications in heterogeneous catalysis, ion-recognition, nonlinear optics and molecular adsorption (Bradshaw et al., 2005; Das & Bharadwaj, 2009; Hua et al., 2010). One of the effective strategies for construction of such polymers is to select suitable multidentate organic ligands as building blocks to link metal centers into infinite framework. Among popularly employed organic ligands, N–, or O– multidentate donor ligands are regarded as excellent candidates for building the blocks of desirable frameworks (Peng et al., 2010). Herein, we report the crystal structure of the title coordination polymer.

The asymmetric unit of the title complex consists of half of a nickel ion, a 3,5-bis(pyridin-4-ylmethylamino)benzoate anion, a coordinated water molecule, and one half water molecule of crystallization. The Ni ion is located on an inversion center and coordinated by two carboxylate O atoms from two different 3,5-bis(pyridin-4-ylmethylamino)benzoate anions, two O atoms from two coordinated water molecules, and two N atoms from two different 3,5-bis(pyridin-4-ylmethylamino)benzoate anions, displaying a slightly distorted NiN₂O₄ octahedral geometry. (Fig. 1). Each 3,5-bis(pyridin-4-ylmethylamino)benzoate anion acts as a µ₂-bridge, linking different nickel ions to form a one-dimensional chain (Fig. 2). In the crystal structure, adjacent chains are further linked through N—H···O, O—H···O, O—H···N and C—H···O hydrogen bonds into a three-dimensional network (Fig. 3 and Table 1). Water molecules as donor or acceptor, including coordinated water molecules and lattice water molecule, play very important roles in the formation of these hydrogen bonding interactions.

Related literature top

For background to metal-organic hybrid materials, see: Bradshaw et al. (2005); Das & Bharadwaj (2009); Hua et al. (2010). For the use of N-, or O- multidentate donor ligands as building blocks in the construction of infinite frameworks, see: Peng et al. (2010).For related structures, see: Chen et al. (2009); Kuai et al. (2011). Scheme – should show 2 waters and 2 organic ligands per Ni atom

Experimental top

A mixture of nickel nitrate hexahydrate (29.1 mg, 0.1 mmol), 3,5-bis(pyridin-4-ylmethylamino)benzoic acid (33.4 mg, 0.1 mmol), and potassium hydroxide (5.61 mg, 0.1 mmol) in 8 ml H₂O was sealed in a 16 ml Teflon-lined stainless steel container and heated to 373 K for 3 days. After cooling to the room temperature, green block crystals of the title complex were obtained.

Structure description top

For background to metal-organic hybrid materials, see: Bradshaw et al. (2005); Das & Bharadwaj (2009); Hua et al. (2010). For the use of N-, or O- multidentate donor ligands as building blocks in the construction of infinite frameworks, see: Peng et al. (2010).For related structures, see: Chen et al. (2009); Kuai et al. (2011). Scheme – should show 2 waters and 2 organic ligands per Ni atom

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination environment of nickel ion in the title complex with the ellipsoids drawn at the 30% probability level; hydrogen atoms have been omitted for clarity. Symmetry codes: (A) x, 1 + y, z; (B) -x, 1 - y, 1 - z; (C) -x, 2 - y, 1 - z.
	Fig. 2. A one-dimensional chain formed from nickel ions and 3,5-bis(pyridin-4-ylmethylamino)benzoate anions.
	Fig. 3. Unit cell packing of the title complex showing the three-dimensional network constructed from one-dimensional chains via hydrogen bonding.

catena-Poly[[diaquabis{µ₂-3,5-bis[(pyridin-4-yl)methylamino]benzoato}nickel] monohydrate] top

Crystal data top

[Ni(C₁₉H₁₇N₄O₂)₂(H₂O)₂]·H₂O	F(000) = 816
M_r = 779.49	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2160 reflections
a = 10.7786 (10) Å	θ = 2.5–22.6°
b = 9.3152 (9) Å	µ = 0.60 mm⁻¹
c = 18.1211 (17) Å	T = 293 K
β = 92.324 (1)°	Block, green
V = 1817.9 (3) Å³	0.22 × 0.20 × 0.18 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	4300 independent reflections
Radiation source: fine-focus sealed tube	2688 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 28.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADBAS; Sheldrick, 1996)	h = −14→11
T_min = 0.880, T_max = 0.900	k = −12→11
11129 measured reflections	l = −23→23

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0321P)²] where P = (F_o² + 2F_c²)/3
4300 reflections	(Δ/σ)_max < 0.001
250 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Ni(C₁₉H₁₇N₄O₂)₂(H₂O)₂]·H₂O	V = 1817.9 (3) Å³
M_r = 779.49	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.7786 (10) Å	µ = 0.60 mm⁻¹
b = 9.3152 (9) Å	T = 293 K
c = 18.1211 (17) Å	0.22 × 0.20 × 0.18 mm
β = 92.324 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4300 independent reflections
Absorption correction: multi-scan (SADBAS; Sheldrick, 1996)	2688 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.900	R_int = 0.061
11129 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 0.90	Δρ_max = 0.44 e Å⁻³
4300 reflections	Δρ_min = −0.47 e Å⁻³
250 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.2314 (2)	0.6148 (2)	0.75121 (13)	0.0339 (6)
C2	0.3407 (2)	0.6653 (3)	0.78657 (13)	0.0378 (6)
H1	0.3675	0.6260	0.8316	0.045*
C3	0.4095 (2)	0.7733 (3)	0.75505 (13)	0.0377 (6)
C4	0.3705 (2)	0.8302 (3)	0.68700 (13)	0.0394 (6)
H2	0.4173	0.9009	0.6650	0.047*
C5	0.2619 (2)	0.7814 (2)	0.65213 (12)	0.0324 (5)
C6	0.1920 (2)	0.6747 (2)	0.68380 (12)	0.0327 (5)
H3	0.1189	0.6430	0.6601	0.039*
C12	0.1299 (2)	0.1913 (2)	0.61577 (12)	0.0344 (6)
H4	0.1999	0.1400	0.6032	0.041*
C13	0.1411 (2)	0.2878 (2)	0.67343 (12)	0.0359 (6)
H5	0.2170	0.2994	0.6990	0.043*
C14	0.0392 (2)	0.3673 (2)	0.69312 (12)	0.0323 (5)
C15	−0.0692 (2)	0.3470 (2)	0.65150 (13)	0.0390 (6)
H6	−0.1396	0.4001	0.6616	0.047*
C16	−0.0735 (2)	0.2485 (3)	0.59503 (13)	0.0389 (6)
H7	−0.1479	0.2371	0.5678	0.047*
C17	0.0430 (2)	0.4665 (2)	0.75874 (13)	0.0389 (6)
H8	−0.0025	0.5533	0.7456	0.047*
H9	0.0009	0.4206	0.7987	0.047*
C32	0.2739 (3)	1.0393 (3)	0.97764 (16)	0.0556 (8)
H11	0.2331	1.0256	1.0213	0.067*
C33	0.3599 (2)	0.9375 (3)	0.95793 (15)	0.0499 (7)
H12	0.3756	0.8582	0.9880	0.060*
C34	0.4219 (2)	0.9538 (3)	0.89414 (15)	0.0429 (6)
C35	0.3910 (3)	1.0717 (3)	0.85121 (17)	0.0646 (9)
H13	0.4277	1.0856	0.8062	0.078*
C36	0.3051 (3)	1.1692 (3)	0.87565 (19)	0.0748 (10)
H14	0.2877	1.2495	0.8466	0.090*
C37	0.5200 (2)	0.8495 (3)	0.87000 (15)	0.0549 (8)
H15	0.6009	0.8861	0.8861	0.066*
H16	0.5081	0.7587	0.8949	0.066*
C51	0.2157 (2)	0.8553 (2)	0.58246 (13)	0.0325 (5)
N11	0.02360 (17)	0.16775 (19)	0.57703 (10)	0.0312 (4)
N12	0.16700 (19)	0.5057 (2)	0.78483 (10)	0.0402 (5)
H10	0.1781	0.4972	0.8355	0.048*
N31	0.2462 (2)	1.1551 (3)	0.93783 (14)	0.0618 (7)
N32	0.52039 (17)	0.8233 (2)	0.79128 (12)	0.0503 (6)
H17	0.5447	0.8995	0.7696	0.060*
Ni1	0.0000	1.0000	0.5000	0.02782 (13)
O1	0.09988 (14)	0.86368 (16)	0.57090 (8)	0.0344 (4)
O2	0.29410 (15)	0.9082 (2)	0.54080 (10)	0.0502 (5)
O3	0.15872 (13)	1.06418 (16)	0.44745 (8)	0.0342 (4)
H18	0.2116	1.0178	0.4756	0.041*
H19	0.1664	1.1683	0.4476	0.041*
O4	0.4743 (5)	−0.0193 (9)	0.4494 (3)	0.204 (4)	0.50
H20	0.4269	−0.0406	0.4985	0.245*	0.50
H21	0.5132	0.0652	0.4551	0.245*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0435 (14)	0.0271 (13)	0.0308 (13)	0.0031 (11)	−0.0003 (11)	−0.0066 (10)
C2	0.0454 (15)	0.0369 (15)	0.0302 (14)	0.0113 (12)	−0.0078 (11)	−0.0043 (11)
C3	0.0293 (13)	0.0405 (15)	0.0427 (15)	0.0071 (11)	−0.0058 (11)	−0.0113 (12)
C4	0.0347 (14)	0.0393 (15)	0.0441 (16)	0.0011 (11)	−0.0009 (12)	−0.0003 (12)
C5	0.0333 (13)	0.0313 (13)	0.0323 (13)	0.0051 (10)	−0.0006 (10)	−0.0001 (10)
C6	0.0356 (13)	0.0312 (13)	0.0310 (13)	0.0009 (10)	−0.0038 (10)	−0.0028 (10)
C12	0.0332 (13)	0.0323 (14)	0.0380 (14)	−0.0011 (11)	0.0047 (11)	−0.0062 (11)
C13	0.0360 (14)	0.0371 (14)	0.0345 (14)	−0.0082 (11)	0.0002 (11)	−0.0060 (11)
C14	0.0426 (14)	0.0250 (13)	0.0297 (13)	−0.0068 (11)	0.0069 (11)	0.0010 (10)
C15	0.0398 (14)	0.0313 (14)	0.0458 (16)	0.0050 (11)	0.0023 (12)	−0.0061 (11)
C16	0.0354 (14)	0.0368 (15)	0.0439 (16)	0.0017 (11)	−0.0064 (12)	−0.0030 (11)
C17	0.0548 (16)	0.0313 (15)	0.0313 (14)	−0.0065 (11)	0.0106 (12)	−0.0029 (10)
C32	0.0563 (19)	0.064 (2)	0.0470 (18)	−0.0080 (15)	0.0080 (14)	−0.0100 (15)
C33	0.0539 (18)	0.0496 (17)	0.0457 (17)	−0.0045 (14)	−0.0064 (14)	−0.0002 (14)
C34	0.0396 (15)	0.0410 (16)	0.0476 (17)	−0.0071 (12)	−0.0042 (13)	−0.0096 (13)
C35	0.085 (2)	0.0425 (18)	0.069 (2)	−0.0043 (17)	0.0315 (18)	−0.0008 (16)
C36	0.108 (3)	0.0388 (18)	0.079 (2)	0.0121 (18)	0.028 (2)	0.0042 (16)
C37	0.0401 (16)	0.069 (2)	0.0540 (19)	0.0042 (14)	−0.0149 (13)	−0.0180 (15)
C51	0.0373 (14)	0.0279 (13)	0.0321 (14)	0.0001 (11)	−0.0007 (11)	−0.0008 (10)
N11	0.0333 (11)	0.0293 (11)	0.0310 (11)	−0.0016 (9)	−0.0002 (8)	−0.0021 (8)
N12	0.0643 (14)	0.0322 (11)	0.0237 (10)	−0.0067 (11)	−0.0039 (9)	−0.0009 (9)
N31	0.0758 (18)	0.0476 (16)	0.0629 (17)	0.0067 (13)	0.0152 (14)	−0.0085 (13)
N32	0.0350 (12)	0.0637 (16)	0.0515 (14)	0.0028 (11)	−0.0086 (10)	−0.0131 (12)
Ni1	0.0319 (2)	0.0265 (2)	0.0248 (2)	−0.00238 (19)	−0.00169 (16)	−0.00021 (18)
O1	0.0327 (9)	0.0358 (10)	0.0340 (9)	−0.0021 (7)	−0.0056 (7)	0.0060 (7)
O2	0.0358 (10)	0.0643 (13)	0.0509 (12)	−0.0005 (9)	0.0071 (8)	0.0203 (10)
O3	0.0401 (10)	0.0308 (9)	0.0313 (9)	−0.0035 (7)	−0.0020 (7)	0.0042 (7)
O4	0.126 (5)	0.383 (11)	0.105 (5)	−0.158 (6)	0.030 (4)	−0.026 (6)

Geometric parameters (Å, º) top

C1—N12	1.386 (3)	C32—H11	0.9300
C1—C6	1.393 (3)	C33—C34	1.367 (3)
C1—C2	1.400 (3)	C33—H12	0.9300
C2—C3	1.387 (3)	C34—C35	1.379 (4)
C2—H1	0.9300	C34—C37	1.514 (3)
C3—C4	1.392 (3)	C35—C36	1.383 (4)
C3—N32	1.418 (3)	C35—H13	0.9300
C4—C5	1.383 (3)	C36—N31	1.322 (3)
C4—H2	0.9300	C36—H14	0.9300
C5—C6	1.386 (3)	C37—N32	1.447 (3)
C5—C51	1.505 (3)	C37—H15	0.9700
C6—H3	0.9300	C37—H16	0.9700
C12—N11	1.337 (3)	C51—O2	1.256 (3)
C12—C13	1.380 (3)	C51—O1	1.260 (3)
C12—H4	0.9300	N11—Ni1ⁱ	2.1038 (18)
C13—C14	1.383 (3)	N12—H10	0.9247
C13—H5	0.9300	N32—H17	0.8583
C14—C15	1.378 (3)	Ni1—O1ⁱⁱ	2.0761 (15)
C14—C17	1.505 (3)	Ni1—O1	2.0761 (15)
C15—C16	1.374 (3)	Ni1—O3	2.0792 (14)
C15—H6	0.9300	Ni1—O3ⁱⁱ	2.0792 (14)
C16—N11	1.340 (3)	Ni1—N11ⁱⁱⁱ	2.1038 (18)
C16—H7	0.9300	Ni1—N11^iv	2.1038 (18)
C17—N12	1.446 (3)	O3—H18	0.8647
C17—H8	0.9700	O3—H19	0.9729
C17—H9	0.9700	O4—H20	1.0633
C32—N31	1.325 (3)	O4—H21	0.8961
C32—C33	1.383 (4)

N12—C1—C6	122.6 (2)	C35—C34—C37	120.2 (3)
N12—C1—C2	118.2 (2)	C34—C35—C36	119.5 (3)
C6—C1—C2	119.2 (2)	C34—C35—H13	120.3
C3—C2—C1	120.6 (2)	C36—C35—H13	120.3
C3—C2—H1	119.7	N31—C36—C35	124.0 (3)
C1—C2—H1	119.7	N31—C36—H14	118.0
C2—C3—C4	119.6 (2)	C35—C36—H14	118.0
C2—C3—N32	120.1 (2)	N32—C37—C34	115.0 (2)
C4—C3—N32	120.3 (2)	N32—C37—H15	108.5
C5—C4—C3	120.0 (2)	C34—C37—H15	108.5
C5—C4—H2	120.0	N32—C37—H16	108.5
C3—C4—H2	120.0	C34—C37—H16	108.5
C4—C5—C6	120.7 (2)	H15—C37—H16	107.5
C4—C5—C51	118.5 (2)	O2—C51—O1	124.2 (2)
C6—C5—C51	120.6 (2)	O2—C51—C5	118.4 (2)
C5—C6—C1	119.9 (2)	O1—C51—C5	117.4 (2)
C5—C6—H3	120.1	C12—N11—C16	116.2 (2)
C1—C6—H3	120.1	C12—N11—Ni1ⁱ	123.26 (15)
N11—C12—C13	123.5 (2)	C16—N11—Ni1ⁱ	120.24 (15)
N11—C12—H4	118.3	C1—N12—C17	120.95 (19)
C13—C12—H4	118.3	C1—N12—H10	116.9
C12—C13—C14	119.8 (2)	C17—N12—H10	112.6
C12—C13—H5	120.1	C36—N31—C32	116.0 (3)
C14—C13—H5	120.1	C3—N32—C37	118.4 (2)
C15—C14—C13	116.8 (2)	C3—N32—H17	109.1
C15—C14—C17	120.8 (2)	C37—N32—H17	109.0
C13—C14—C17	122.4 (2)	O1ⁱⁱ—Ni1—O1	180.00 (7)
C16—C15—C14	120.1 (2)	O1ⁱⁱ—Ni1—O3	87.50 (6)
C16—C15—H6	120.0	O1—Ni1—O3	92.50 (6)
C14—C15—H6	120.0	O1ⁱⁱ—Ni1—O3ⁱⁱ	92.50 (6)
N11—C16—C15	123.6 (2)	O1—Ni1—O3ⁱⁱ	87.50 (6)
N11—C16—H7	118.2	O3—Ni1—O3ⁱⁱ	180.0
C15—C16—H7	118.2	O1ⁱⁱ—Ni1—N11ⁱⁱⁱ	89.89 (7)
N12—C17—C14	114.09 (19)	O1—Ni1—N11ⁱⁱⁱ	90.11 (7)
N12—C17—H8	108.7	O3—Ni1—N11ⁱⁱⁱ	89.39 (6)
C14—C17—H8	108.7	O3ⁱⁱ—Ni1—N11ⁱⁱⁱ	90.61 (6)
N12—C17—H9	108.7	O1ⁱⁱ—Ni1—N11^iv	90.11 (7)
C14—C17—H9	108.7	O1—Ni1—N11^iv	89.89 (7)
H8—C17—H9	107.6	O3—Ni1—N11^iv	90.61 (6)
N31—C32—C33	123.8 (3)	O3ⁱⁱ—Ni1—N11^iv	89.39 (6)
N31—C32—H11	118.1	N11ⁱⁱⁱ—Ni1—N11^iv	180.00 (7)
C33—C32—H11	118.1	C51—O1—Ni1	128.76 (15)
C34—C33—C32	119.9 (3)	Ni1—O3—H18	96.9
C34—C33—H12	120.1	Ni1—O3—H19	110.9
C32—C33—H12	120.1	H18—O3—H19	116.3
C33—C34—C35	116.8 (3)	H20—O4—H21	107.8
C33—C34—C37	123.0 (3)

N12—C1—C2—C3	179.4 (2)	C33—C34—C37—N32	142.8 (3)
C6—C1—C2—C3	−0.1 (3)	C35—C34—C37—N32	−37.1 (4)
C1—C2—C3—C4	−1.1 (3)	C4—C5—C51—O2	31.6 (3)
C1—C2—C3—N32	−179.8 (2)	C6—C5—C51—O2	−153.6 (2)
C2—C3—C4—C5	1.6 (4)	C4—C5—C51—O1	−146.4 (2)
N32—C3—C4—C5	−179.7 (2)	C6—C5—C51—O1	28.4 (3)
C3—C4—C5—C6	−0.9 (4)	C13—C12—N11—C16	2.7 (3)
C3—C4—C5—C51	174.0 (2)	C13—C12—N11—Ni1ⁱ	−170.66 (17)
C4—C5—C6—C1	−0.4 (3)	C15—C16—N11—C12	−2.4 (4)
C51—C5—C6—C1	−175.1 (2)	C15—C16—N11—Ni1ⁱ	171.21 (18)
N12—C1—C6—C5	−178.6 (2)	C6—C1—N12—C17	−11.8 (3)
C2—C1—C6—C5	0.9 (3)	C2—C1—N12—C17	168.7 (2)
N11—C12—C13—C14	−0.8 (4)	C14—C17—N12—C1	82.0 (3)
C12—C13—C14—C15	−1.6 (3)	C35—C36—N31—C32	0.1 (5)
C12—C13—C14—C17	175.6 (2)	C33—C32—N31—C36	0.9 (4)
C13—C14—C15—C16	2.0 (3)	C2—C3—N32—C37	−44.2 (3)
C17—C14—C15—C16	−175.3 (2)	C4—C3—N32—C37	137.1 (3)
C14—C15—C16—N11	0.1 (4)	C34—C37—N32—C3	−56.3 (3)
C15—C14—C17—N12	−164.7 (2)	O2—C51—O1—Ni1	−16.3 (3)
C13—C14—C17—N12	18.1 (3)	C5—C51—O1—Ni1	161.54 (15)
N31—C32—C33—C34	0.0 (4)	O1ⁱⁱ—Ni1—O1—C51	−87 (100)
C32—C33—C34—C35	−1.9 (4)	O3—Ni1—O1—C51	12.11 (19)
C32—C33—C34—C37	178.1 (2)	O3ⁱⁱ—Ni1—O1—C51	−167.89 (19)
C33—C34—C35—C36	2.9 (4)	N11ⁱⁱⁱ—Ni1—O1—C51	101.51 (19)
C37—C34—C35—C36	−177.2 (3)	N11^iv—Ni1—O1—C51	−78.49 (19)
C34—C35—C36—N31	−2.0 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N12—H10···O3^v	0.92	2.13	3.023 (2)	163
O3—H18···O2	0.86	1.77	2.627 (2)	169
O4—H21···O2^vi	0.90	2.09	2.701 (5)	125
O4—H20···O2ⁱ	1.06	1.72	2.690 (5)	150
O3—H19···N31^vii	0.97	1.87	2.787 (3)	156
C2—H1···O4^viii	0.93	2.58	3.505 (6)	172
C37—H16···O4^viii	0.97	2.47	3.440 (8)	176

Symmetry codes: (i) x, y−1, z; (v) x, −y+3/2, z+1/2; (vi) −x+1, −y+1, −z+1; (vii) x, −y+5/2, z−1/2; (viii) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₉H₁₇N₄O₂)₂(H₂O)₂]·H₂O
M_r	779.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.7786 (10), 9.3152 (9), 18.1211 (17)
β (°)	92.324 (1)
V (Å³)	1817.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADBAS; Sheldrick, 1996)
T_min, T_max	0.880, 0.900
No. of measured, independent and observed [I > 2σ(I)] reflections	11129, 4300, 2688
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.094, 0.90
No. of reflections	4300
No. of parameters	250
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.47

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N12—H10···O3ⁱ	0.92	2.13	3.023 (2)	163.1
O3—H18···O2	0.86	1.77	2.627 (2)	169.0
O4—H21···O2ⁱⁱ	0.90	2.09	2.701 (5)	124.6
O4—H20···O2ⁱⁱⁱ	1.06	1.72	2.690 (5)	149.6
O3—H19···N31^iv	0.97	1.87	2.787 (3)	156.4
C2—H1···O4^v	0.93	2.58	3.505 (6)	172.0
C37—H16···O4^v	0.97	2.47	3.440 (8)	176.0

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x, −y+5/2, z−1/2; (v) x, −y+1/2, z+1/2.

Acknowledgements

The authors gratefully acknowledge the Natural Science Foundation of Jiangsu Province of China (BK2008195) for financial support of this work.

References

Bradshaw, D., Claridge, J. B., Cussen, E. J., Prior, T. J. & Rosseinsky, M. J. (2005). Acc. Chem. Res. 38, 273–282. Web of Science CrossRef PubMed CAS Google Scholar
Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, M.-S., Chen, S.-S., Okamura, T.-A., Su, Z., Sun, W.-Y. & Ueyama, N. (2009). J. Coord. Chem. 62, 2421–2428. Web of Science CSD CrossRef CAS Google Scholar
Das, M. C. & Bharadwaj, P. K. (2009). J. Am. Chem. Soc. 131, 10942–10943. Web of Science CSD CrossRef PubMed CAS Google Scholar
Hua, Q., Zhao, Y., Xu, G.-C., Chen, M.-S., Su, Z., Cai, K. & Sun, W.-Y. (2010). Cryst. Growth Des. 10, 2553–2562. Web of Science CSD CrossRef CAS Google Scholar
Kuai, H.-W., Cheng, X.-C. & Zhu, X.-H. (2011). J. Coord. Chem. 64, 1636–1644. Web of Science CSD CrossRef Google Scholar
Peng, G., Qiu, Y.-C., Liu, Z.-H., Liu, B. & Deng, H. (2010). Cryst. Growth Des. 10, 114–121. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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