Diaqua-bis(N,N-diethyl-nicotinamide-κN)bis-[4-(dimethyl-amino)benzoato-κO]nickel(II).

The centrosymmetric title Ni(II) complex, [Ni(C(9)H(10)NO(2))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], contains two dimethyl-amino-benzoate (DMAB), two diethyl-nicotinamide (DENA) ligands and two water mol-ecules, all of them monodentate. The four O atoms in the equatorial plane around the Ni(II) atom form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two pyridine N atoms of the DENA ligands in axial positions. The Ni(II) atom is displaced by 0.681 (1) Å out of the least-squares plane of the carboxyl-ate group. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 5.61 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 73.20 (4)°. An intra-molecular O-H⋯O hydrogen bond results in the formation of a six-membered ring with a twisted conformation. In the crystal structure, inter-molecular O-H⋯O and C-H⋯O hydrogen bonds link mol-ecules into a three-dimensional network. Two weak C-H⋯π inter-actions are also present.

Related literature

For our ongoing investigations of the transition metal complexes of nicotinamide, and/or the nicotinic acid derivative N,N-diethyl­nicotinamide, an important respiratory stimulant, see: Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶). For related structures, see: Hökelek et al. (2009 ▶); Sertçelik et al. (2009 ▶).

Experimental

Crystal data

[Ni(C9H10NO2)2(C10H14N2O)2(H2O)2]

M = 779.57

Monoclinic,

a = 6.5081 (1) Å

b = 20.3157 (3) Å

c = 14.7235 (2) Å

β = 98.487 (2)°

V = 1925.37 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.56 mm−1

T = 100 K

0.53 × 0.43 × 0.28 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.751, T max = 0.851

18748 measured reflections

4819 independent reflections

4332 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.076

S = 1.04

4819 reflections

253 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.41 e Å−3

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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030098/xu2570sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030098/xu2570Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C9H10NO2)2(C10H14N2O)2(H2O)2]	F(000) = 828
Mr = 779.57	Dx = 1.345 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9995 reflections
a = 6.5081 (1) Å	θ = 2.4–28.4°
b = 20.3157 (3) Å	µ = 0.56 mm−1
c = 14.7235 (2) Å	T = 100 K
β = 98.487 (2)°	Block, blue
V = 1925.37 (5) Å3	0.53 × 0.43 × 0.28 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	4819 independent reflections
Radiation source: fine-focus sealed tube	4332 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.751, Tmax = 0.851	k = −25→27
18748 measured reflections	l = −19→19

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0382P)2 + 0.8491P] where P = (Fo2 + 2Fc2)/3
4819 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.01159 (6)
O1	0.46213 (13)	0.50364 (4)	0.63567 (6)	0.01499 (17)
O2	0.12365 (13)	0.52742 (4)	0.62891 (5)	0.01770 (17)
O3	0.24871 (14)	0.28574 (5)	0.24645 (6)	0.02031 (19)
O4	0.21205 (14)	0.54434 (4)	0.46008 (6)	0.01635 (17)
H41	0.122 (3)	0.5242 (11)	0.4234 (13)	0.039 (5)*
H42	0.169 (3)	0.5441 (9)	0.5121 (14)	0.039 (5)*
N1	0.37272 (15)	0.40504 (5)	0.48904 (6)	0.01379 (19)
N2	−0.07839 (16)	0.27925 (5)	0.28157 (7)	0.0179 (2)
N3	0.31666 (19)	0.39407 (6)	1.02652 (7)	0.0242 (2)
C1	0.29426 (19)	0.50566 (5)	0.66964 (7)	0.0135 (2)
C2	0.30181 (18)	0.47867 (6)	0.76460 (7)	0.0145 (2)
C3	0.12187 (19)	0.47318 (6)	0.80487 (8)	0.0177 (2)
H3	−0.0035	0.4882	0.7731	0.021*
C4	0.1257 (2)	0.44578 (6)	0.89121 (8)	0.0197 (2)
H4	0.0029	0.4423	0.9161	0.024*
C5	0.3124 (2)	0.42317 (6)	0.94177 (8)	0.0182 (2)
C6	0.4949 (2)	0.43026 (7)	0.90178 (8)	0.0204 (2)
H6	0.6216	0.4170	0.9342	0.024*
C7	0.48766 (19)	0.45671 (6)	0.81467 (8)	0.0177 (2)
H7	0.6096	0.4599	0.7890	0.021*
C8	0.28565 (18)	0.38146 (6)	0.40728 (7)	0.0142 (2)
H8	0.2801	0.4084	0.3559	0.017*
C9	0.20358 (18)	0.31856 (6)	0.39614 (7)	0.0141 (2)
C10	0.21297 (19)	0.27802 (6)	0.47281 (8)	0.0174 (2)
H10	0.1598	0.2355	0.4673	0.021*
C11	0.30290 (19)	0.30200 (6)	0.55766 (8)	0.0176 (2)
H11	0.3104	0.2760	0.6100	0.021*
C12	0.38123 (18)	0.36540 (6)	0.56268 (7)	0.0158 (2)
H12	0.4425	0.3813	0.6195	0.019*
C13	0.12500 (19)	0.29353 (6)	0.30122 (8)	0.0149 (2)
C14	−0.2321 (2)	0.29609 (7)	0.34147 (9)	0.0241 (3)
H14A	−0.3490	0.3180	0.3053	0.029*
H14B	−0.1700	0.3268	0.3880	0.029*
C15	−0.3107 (2)	0.23647 (9)	0.38829 (12)	0.0381 (4)
H15A	−0.3958	0.2508	0.4325	0.057*
H15B	−0.1947	0.2119	0.4188	0.057*
H15C	−0.3912	0.2091	0.3432	0.057*
C16	−0.1508 (2)	0.24500 (7)	0.19478 (9)	0.0234 (3)
H16A	−0.0881	0.2653	0.1459	0.028*
H16B	−0.3002	0.2500	0.1800	0.028*
C17	−0.0974 (2)	0.17227 (7)	0.19917 (10)	0.0292 (3)
H17A	−0.1409	0.1525	0.1402	0.044*
H17B	−0.1673	0.1513	0.2444	0.044*
H17C	0.0500	0.1670	0.2157	0.044*
C18	0.1327 (3)	0.39476 (7)	1.07082 (9)	0.0301 (3)
H18A	0.1616	0.3730	1.1292	0.045*
H18B	0.0219	0.3723	1.0328	0.045*
H18C	0.0924	0.4395	1.0799	0.045*
C19	0.5140 (2)	0.37889 (7)	1.08181 (9)	0.0273 (3)
H19A	0.4902	0.3617	1.1401	0.041*
H19B	0.5962	0.4182	1.0913	0.041*
H19C	0.5863	0.3468	1.0507	0.041*

	U11	U22	U33	U12	U13	U23
Ni1	0.01140 (11)	0.01277 (11)	0.01029 (10)	−0.00191 (7)	0.00061 (7)	0.00090 (7)
O1	0.0140 (4)	0.0182 (4)	0.0128 (4)	−0.0029 (3)	0.0018 (3)	0.0004 (3)
O2	0.0151 (4)	0.0226 (4)	0.0150 (4)	0.0013 (3)	0.0009 (3)	0.0008 (3)
O3	0.0219 (5)	0.0234 (5)	0.0160 (4)	−0.0044 (4)	0.0040 (3)	−0.0023 (3)
O4	0.0145 (4)	0.0197 (4)	0.0143 (4)	−0.0009 (3)	0.0006 (3)	0.0025 (3)
N1	0.0130 (5)	0.0144 (5)	0.0139 (4)	−0.0008 (4)	0.0018 (3)	0.0009 (3)
N2	0.0162 (5)	0.0170 (5)	0.0192 (5)	−0.0022 (4)	−0.0016 (4)	−0.0012 (4)
N3	0.0285 (6)	0.0277 (6)	0.0172 (5)	0.0012 (5)	0.0058 (4)	0.0072 (4)
C1	0.0165 (5)	0.0112 (5)	0.0125 (5)	−0.0029 (4)	0.0012 (4)	−0.0020 (4)
C2	0.0171 (6)	0.0140 (5)	0.0125 (5)	−0.0016 (4)	0.0027 (4)	−0.0008 (4)
C3	0.0159 (6)	0.0204 (6)	0.0168 (5)	0.0008 (5)	0.0024 (4)	0.0011 (4)
C4	0.0189 (6)	0.0223 (6)	0.0194 (5)	−0.0004 (5)	0.0077 (4)	0.0022 (4)
C5	0.0245 (6)	0.0159 (5)	0.0147 (5)	−0.0004 (5)	0.0042 (4)	0.0010 (4)
C6	0.0187 (6)	0.0242 (6)	0.0177 (5)	0.0030 (5)	0.0009 (4)	0.0038 (4)
C7	0.0157 (6)	0.0208 (6)	0.0174 (5)	0.0005 (5)	0.0044 (4)	0.0021 (4)
C8	0.0134 (5)	0.0156 (5)	0.0135 (5)	−0.0004 (4)	0.0021 (4)	0.0019 (4)
C9	0.0129 (5)	0.0153 (5)	0.0142 (5)	−0.0001 (4)	0.0018 (4)	−0.0004 (4)
C10	0.0194 (6)	0.0138 (5)	0.0193 (5)	−0.0021 (4)	0.0036 (4)	0.0017 (4)
C11	0.0202 (6)	0.0174 (6)	0.0154 (5)	0.0007 (5)	0.0030 (4)	0.0041 (4)
C12	0.0160 (6)	0.0183 (6)	0.0129 (5)	0.0009 (4)	0.0009 (4)	0.0010 (4)
C13	0.0179 (6)	0.0103 (5)	0.0158 (5)	−0.0018 (4)	−0.0003 (4)	0.0014 (4)
C14	0.0156 (6)	0.0278 (7)	0.0285 (6)	0.0027 (5)	0.0018 (5)	0.0014 (5)
C15	0.0214 (7)	0.0479 (10)	0.0471 (9)	0.0047 (7)	0.0118 (6)	0.0191 (7)
C16	0.0233 (7)	0.0214 (6)	0.0223 (6)	−0.0049 (5)	−0.0066 (5)	−0.0020 (5)
C17	0.0324 (8)	0.0206 (7)	0.0331 (7)	−0.0061 (6)	−0.0004 (6)	−0.0057 (5)
C18	0.0427 (9)	0.0274 (7)	0.0238 (6)	0.0071 (6)	0.0174 (6)	0.0082 (5)
C19	0.0373 (8)	0.0272 (7)	0.0166 (5)	0.0057 (6)	0.0016 (5)	0.0050 (5)

Ni1—O1	2.0498 (8)	C8—H8	0.9300
Ni1—O1i	2.0498 (8)	C9—C8	1.3853 (16)
Ni1—O4	2.0842 (9)	C9—C10	1.3915 (15)
Ni1—O4i	2.0842 (9)	C9—C13	1.5042 (15)
Ni1—N1	2.0962 (10)	C10—H10	0.9300
Ni1—N1i	2.0962 (10)	C11—C10	1.3874 (16)
O1—C1	1.2675 (14)	C11—C12	1.3831 (17)
O2—C1	1.2615 (15)	C11—H11	0.9300
O3—C13	1.2309 (15)	C12—H12	0.9300
O4—H41	0.84 (2)	C14—H14A	0.9700
O4—H42	0.85 (2)	C14—H14B	0.9700
N1—C8	1.3411 (14)	C15—C14	1.519 (2)
N1—C12	1.3452 (14)	C15—H15A	0.9600
N2—C13	1.3443 (16)	C15—H15B	0.9600
N2—C14	1.4682 (16)	C15—H15C	0.9600
N3—C18	1.4457 (17)	C16—N2	1.4700 (15)
N3—C19	1.4485 (18)	C16—H16A	0.9700
C2—C1	1.4958 (15)	C16—H16B	0.9700
C2—C7	1.3937 (17)	C17—C16	1.5173 (19)
C3—C2	1.3930 (16)	C17—H17A	0.9600
C3—C4	1.3846 (16)	C17—H17B	0.9600
C3—H3	0.9300	C17—H17C	0.9600
C4—H4	0.9300	C18—H18A	0.9600
C5—N3	1.3773 (15)	C18—H18B	0.9600
C5—C4	1.4050 (18)	C18—H18C	0.9600
C5—C6	1.4086 (17)	C19—H19A	0.9600
C6—C7	1.3850 (16)	C19—H19B	0.9600
C6—H6	0.9300	C19—H19C	0.9600
C7—H7	0.9300
O1—Ni1—O1i	180.000 (1)	C8—C9—C10	118.69 (10)
O1—Ni1—O4	91.54 (3)	C8—C9—C13	119.61 (10)
O1i—Ni1—O4	88.46 (3)	C10—C9—C13	121.45 (10)
O1—Ni1—O4i	88.46 (3)	C9—C10—H10	120.5
O1i—Ni1—O4i	91.54 (3)	C11—C10—C9	118.99 (11)
O1—Ni1—N1	90.30 (3)	C11—C10—H10	120.5
O1i—Ni1—N1	89.70 (3)	C10—C11—H11	120.7
O1—Ni1—N1i	89.70 (3)	C12—C11—C10	118.58 (10)
O1i—Ni1—N1i	90.30 (3)	C12—C11—H11	120.7
O4—Ni1—O4i	180.0	N1—C12—C11	122.91 (11)
O4—Ni1—N1	92.72 (4)	N1—C12—H12	118.5
O4i—Ni1—N1	87.28 (4)	C11—C12—H12	118.5
O4—Ni1—N1i	87.28 (4)	O3—C13—N2	123.34 (11)
O4i—Ni1—N1i	92.72 (4)	O3—C13—C9	119.12 (11)
N1—Ni1—N1i	180.0	N2—C13—C9	117.51 (10)
C1—O1—Ni1	128.34 (8)	N2—C14—C15	113.05 (12)
Ni1—O4—H41	118.7 (14)	N2—C14—H14A	109.0
Ni1—O4—H42	98.5 (13)	N2—C14—H14B	109.0
H41—O4—H42	106.5 (18)	C15—C14—H14A	109.0
C8—N1—C12	118.12 (10)	C15—C14—H14B	109.0
C8—N1—Ni1	120.51 (7)	H14A—C14—H14B	107.8
C12—N1—Ni1	121.34 (8)	C14—C15—H15A	109.5
C13—N2—C14	123.83 (10)	C14—C15—H15B	109.5
C13—N2—C16	117.93 (10)	C14—C15—H15C	109.5
C14—N2—C16	118.24 (11)	H15A—C15—H15B	109.5
C5—N3—C18	119.82 (11)	H15A—C15—H15C	109.5
C5—N3—C19	119.89 (11)	H15B—C15—H15C	109.5
C18—N3—C19	118.24 (11)	N2—C16—C17	112.45 (11)
O1—C1—C2	116.46 (10)	N2—C16—H16A	109.1
O2—C1—O1	124.98 (10)	N2—C16—H16B	109.1
O2—C1—C2	118.55 (10)	C17—C16—H16A	109.1
C3—C2—C1	120.90 (11)	C17—C16—H16B	109.1
C3—C2—C7	117.88 (10)	H16A—C16—H16B	107.8
C7—C2—C1	121.20 (10)	C16—C17—H17A	109.5
C2—C3—H3	119.3	C16—C17—H17B	109.5
C4—C3—C2	121.37 (11)	C16—C17—H17C	109.5
C4—C3—H3	119.3	H17A—C17—H17B	109.5
C3—C4—C5	121.00 (11)	H17A—C17—H17C	109.5
C3—C4—H4	119.5	H17B—C17—H17C	109.5
C5—C4—H4	119.5	N3—C18—H18A	109.5
N3—C5—C4	121.38 (11)	N3—C18—H18B	109.5
N3—C5—C6	121.13 (12)	N3—C18—H18C	109.5
C4—C5—C6	117.48 (10)	H18A—C18—H18B	109.5
C5—C6—H6	119.6	H18A—C18—H18C	109.5
C7—C6—C5	120.76 (11)	H18B—C18—H18C	109.5
C7—C6—H6	119.6	N3—C19—H19A	109.5
C2—C7—H7	119.3	N3—C19—H19B	109.5
C6—C7—C2	121.48 (11)	N3—C19—H19C	109.5
C6—C7—H7	119.3	H19A—C19—H19B	109.5
N1—C8—C9	122.70 (10)	H19A—C19—H19C	109.5
N1—C8—H8	118.7	H19B—C19—H19C	109.5
C9—C8—H8	118.7
O4—Ni1—O1—C1	24.97 (9)	C7—C2—C1—O2	−177.04 (11)
O4i—Ni1—O1—C1	−155.03 (9)	C1—C2—C7—C6	−178.48 (11)
N1—Ni1—O1—C1	−67.76 (9)	C3—C2—C7—C6	−0.08 (18)
N1i—Ni1—O1—C1	112.24 (9)	C4—C3—C2—C1	177.32 (11)
O1—Ni1—N1—C8	156.38 (9)	C4—C3—C2—C7	−1.09 (18)
O1i—Ni1—N1—C8	−23.62 (9)	C2—C3—C4—C5	0.7 (2)
O4—Ni1—N1—C8	64.83 (9)	C4—C5—N3—C18	−8.82 (19)
O4i—Ni1—N1—C8	−115.17 (9)	C4—C5—N3—C19	−172.22 (12)
O1—Ni1—N1—C12	−25.63 (9)	C6—C5—N3—C18	172.36 (13)
O1i—Ni1—N1—C12	154.37 (9)	C6—C5—N3—C19	8.97 (19)
O4—Ni1—N1—C12	−117.18 (9)	N3—C5—C4—C3	−178.04 (12)
O4i—Ni1—N1—C12	62.82 (9)	C6—C5—C4—C3	0.81 (19)
Ni1—O1—C1—O2	−25.08 (16)	N3—C5—C6—C7	176.89 (12)
Ni1—O1—C1—C2	153.63 (8)	C4—C5—C6—C7	−1.96 (19)
Ni1—N1—C8—C9	178.55 (8)	C5—C6—C7—C2	1.6 (2)
C12—N1—C8—C9	0.49 (17)	C10—C9—C8—N1	−0.41 (18)
Ni1—N1—C12—C11	−178.58 (9)	C13—C9—C8—N1	−174.79 (11)
C8—N1—C12—C11	−0.54 (17)	C8—C9—C10—C11	0.36 (17)
C14—N2—C13—O3	−171.82 (11)	C13—C9—C10—C11	174.63 (11)
C14—N2—C13—C9	9.85 (17)	C8—C9—C13—O3	64.89 (15)
C16—N2—C13—O3	7.90 (18)	C8—C9—C13—N2	−116.71 (12)
C16—N2—C13—C9	−170.42 (10)	C10—C9—C13—O3	−109.33 (13)
C13—N2—C14—C15	−108.56 (14)	C10—C9—C13—N2	69.07 (15)
C16—N2—C14—C15	71.71 (15)	C12—C11—C10—C9	−0.40 (18)
C3—C2—C1—O1	−174.19 (11)	C10—C11—C12—N1	0.51 (18)
C3—C2—C1—O2	4.60 (17)	C17—C16—N2—C13	76.55 (15)
C7—C2—C1—O1	4.16 (16)	C17—C16—N2—C14	−103.71 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ii	0.84 (2)	1.97 (2)	2.7875 (12)	163 (2)
O4—H42···O2	0.85 (2)	1.82 (2)	2.6552 (12)	165.9 (18)
C11—H11···O3iii	0.93	2.45	3.3641 (15)	167
C18—H18A···O3iv	0.96	2.48	3.4038 (17)	161
C19—H19B···Cg1v	0.96	2.82	3.7203 (15)	157
C15—H15A···Cg2vi	0.96	2.91	3.7575 (16)	148

Table 1

Selected bond lengths (Å)

Ni1—O1	2.0498 (8)
Ni1—O4	2.0842 (9)
Ni1—N1	2.0962 (10)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2i	0.84 (2)	1.97 (2)	2.7875 (12)	163 (2)
O4—H42⋯O2	0.85 (2)	1.82 (2)	2.6552 (12)	165.9 (18)
C11—H11⋯O3ii	0.93	2.45	3.3641 (15)	167
C18—H18A⋯O3iii	0.96	2.48	3.4038 (17)	161
C19—H19B⋯Cg1iv	0.96	2.82	3.7203 (15)	157
C15—H15A⋯Cg2v	0.96	2.91	3.7575 (16)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) . Cg1 and Cg2 are the centroids of the C2–C7 and N1/C8–C12 rings, respectively.