Diaquadi-μ-formato-bis-{μ-2,2'-[propane-1,3-diylbis(nitrilo-methanylyl-idene)]diphenolato}cadmium(II)dinickel(II) dihydrate.

In the centrosymmetric title compound, [CdNi(2)(C(17)H(16)N(2)O(2))(2)(HCOO)(2)(H(2)O)(2)]·2H(2)O, The Ni(II) cation is chelated by a 2,2'-[propane-1,3-diylbis(nitrilo-methanylyl-idene)]diphen-olate (salpn) anion, and further coordinated by a formate anion and a water mol-ecule in a distorted NiN(2)O(4) octa-hedral geometry. The Cd(II) cation, located on an inversion center, is coordinated by four deprotonated hy-droxy groups from two salpn anions and two carboxyl-ate O atoms from formate anions in a distorted octa-hedral geometry. Both formate and salpn anions bridge the Cd and Ni cations, forming a trinuclear complex. Within the salpn anion, the benzene rings are twisted to each other at a dihedral angle of 61.46 (18)°. Inter-molecular O-H⋯O hydrogen bonding is present in the crystal structure. The lattice water mol-ecule is disorder over two positions with an occupancy ratio of 0.75:0.25.

Related literature

For background and applications of metal complexes with Schiff base ligands, see: Niederhoffer et al. (1984 ▶); Tisato et al. (1994 ▶); Yamada (1999 ▶). For the decomposition reaction of solvent DMF, see: Wang et al. (2004 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

[CdNi2(C17H16N2O2)2(HCO2)2(H2O)2]·2H2O

M = 952.56

Triclinic,

a = 9.6769 (9) Å

b = 10.6596 (10) Å

c = 10.7996 (10) Å

α = 72.851 (1)°

β = 63.551 (1)°

γ = 81.478 (1)°

V = 952.87 (15) Å3

Z = 1

Mo Kα radiation

μ = 1.60 mm−1

T = 298 K

0.26 × 0.20 × 0.19 mm

Data collection

Bruker SMART 1000 diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.681, T max = 0.751

4842 measured reflections

3423 independent reflections

2910 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.074

S = 1.06

3423 reflections

259 parameters

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.38 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812029583/xu5190sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029583/xu5190Isup2.hkl

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

[CdNi2(C17H16N2O2)2(HCO2)2(H2O)2]·2H2O	Z = 1
Mr = 952.56	F(000) = 486
Triclinic, P1	Dx = 1.660 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6769 (9) Å	Cell parameters from 2961 reflections
b = 10.6596 (10) Å	θ = 2.4–27.5°
c = 10.7996 (10) Å	µ = 1.60 mm−1
α = 72.851 (1)°	T = 298 K
β = 63.551 (1)°	Block, green
γ = 81.478 (1)°	0.26 × 0.20 × 0.19 mm
V = 952.87 (15) Å3

Bruker SMART 1000 diffractometer	3423 independent reflections
Radiation source: fine-focus sealed tube	2910 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
φ and ω scan	θmax = 25.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
Tmin = 0.681, Tmax = 0.751	k = −12→12
4842 measured reflections	l = −12→11

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.035P)2 + 0.566P] where P = (Fo2 + 2Fc2)/3
3423 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.38 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	Occ. (<1)
Cd1	0.0000	0.5000	1.0000	0.03673 (10)
Ni1	0.14492 (4)	0.34996 (3)	0.74567 (3)	0.03560 (11)
N1	0.3127 (3)	0.3988 (3)	0.5419 (3)	0.0436 (6)
N2	0.1331 (3)	0.1589 (2)	0.7553 (3)	0.0422 (6)
C18	0.3150 (4)	0.3266 (3)	0.9271 (3)	0.0505 (8)
H18	0.4012	0.2946	0.9443	0.061*
C1	0.1565 (3)	0.6410 (3)	0.6481 (3)	0.0400 (6)
C2	0.0920 (4)	0.7624 (3)	0.6718 (3)	0.0513 (8)
H2A	0.0320	0.7688	0.7651	0.062*
C3	0.1151 (4)	0.8742 (3)	0.5589 (4)	0.0612 (9)
H3A	0.0695	0.9538	0.5774	0.073*
C4	0.2056 (5)	0.8674 (4)	0.4197 (4)	0.0648 (10)
H4A	0.2214	0.9421	0.3441	0.078*
C5	0.2714 (4)	0.7498 (4)	0.3942 (3)	0.0564 (9)
H5	0.3332	0.7463	0.3002	0.068*
C6	0.2496 (3)	0.6343 (3)	0.5041 (3)	0.0414 (7)
C7	0.3309 (3)	0.5174 (3)	0.4631 (3)	0.0464 (7)
H7A	0.4049	0.5294	0.3690	0.056*
C8	0.4152 (4)	0.2974 (4)	0.4767 (4)	0.0570 (9)
H8A	0.4948	0.2743	0.5114	0.068*
H8B	0.4655	0.3332	0.3738	0.068*
C9	0.3312 (4)	0.1736 (3)	0.5090 (3)	0.0560 (8)
H9A	0.2448	0.1979	0.4835	0.067*
H9B	0.4010	0.1178	0.4496	0.067*
C10	0.2717 (4)	0.0959 (3)	0.6650 (3)	0.0538 (8)
H10A	0.2475	0.0077	0.6736	0.065*
H10B	0.3515	0.0891	0.6979	0.065*
C11	0.0120 (4)	0.0914 (3)	0.8338 (3)	0.0456 (7)
H11A	0.0181	0.0056	0.8270	0.055*
C12	−0.1348 (3)	0.1337 (3)	0.9328 (3)	0.0413 (6)
C13	−0.2637 (4)	0.0565 (3)	0.9825 (3)	0.0548 (8)
H13A	−0.2512	−0.0186	0.9512	0.066*
C14	−0.4076 (4)	0.0884 (4)	1.0757 (4)	0.0604 (9)
H14A	−0.4920	0.0372	1.1051	0.072*
C15	−0.4247 (4)	0.1982 (4)	1.1251 (3)	0.0561 (8)
H15A	−0.5218	0.2211	1.1879	0.067*
C16	−0.3002 (4)	0.2741 (3)	1.0828 (3)	0.0481 (7)
H16A	−0.3143	0.3455	1.1204	0.058*
C17	−0.1523 (3)	0.2462 (3)	0.9842 (3)	0.0381 (6)
O1	0.1331 (2)	0.53609 (19)	0.75777 (19)	0.0421 (5)
O2	−0.0344 (2)	0.32089 (19)	0.9431 (2)	0.0417 (5)
O3	0.3110 (2)	0.2997 (2)	0.8257 (2)	0.0511 (5)
O4	0.2196 (3)	0.3909 (2)	1.0107 (2)	0.0526 (5)
O5	−0.0232 (2)	0.4059 (2)	0.6516 (2)	0.0500 (5)
H5A	−0.0308	0.4888	0.6383	0.075*
H5B	−0.1151	0.3808	0.7073	0.075*
O6	0.7024 (5)	0.5266 (5)	0.8119 (5)	0.0835 (12)	0.75
H6A	0.6220	0.4853	0.8354	0.125*	0.75
H6B	0.7155	0.5206	0.8862	0.125*	0.75
O6'	0.7860 (15)	0.6031 (14)	0.7325 (14)	0.080 (3)	0.25
H6'A	0.8187	0.6774	0.6749	0.120*	0.25
H6'B	0.7223	0.6136	0.8141	0.120*	0.25

	U11	U22	U33	U12	U13	U23
Cd1	0.04646 (18)	0.03992 (17)	0.02905 (16)	−0.00391 (12)	−0.01648 (13)	−0.01410 (12)
Ni1	0.0396 (2)	0.0408 (2)	0.0300 (2)	−0.00399 (15)	−0.01343 (16)	−0.01492 (15)
N1	0.0385 (13)	0.0612 (17)	0.0360 (13)	−0.0067 (11)	−0.0126 (11)	−0.0221 (12)
N2	0.0485 (14)	0.0436 (14)	0.0400 (13)	0.0036 (11)	−0.0197 (12)	−0.0190 (11)
C18	0.0474 (17)	0.063 (2)	0.0515 (19)	0.0053 (15)	−0.0289 (15)	−0.0198 (16)
C1	0.0450 (16)	0.0472 (17)	0.0335 (14)	−0.0146 (13)	−0.0195 (13)	−0.0074 (12)
C2	0.067 (2)	0.0481 (18)	0.0425 (17)	−0.0047 (15)	−0.0257 (16)	−0.0108 (14)
C3	0.081 (2)	0.050 (2)	0.059 (2)	−0.0018 (17)	−0.039 (2)	−0.0084 (16)
C4	0.084 (3)	0.057 (2)	0.050 (2)	−0.0139 (19)	−0.0354 (19)	0.0084 (17)
C5	0.056 (2)	0.076 (2)	0.0336 (16)	−0.0190 (17)	−0.0180 (15)	−0.0025 (16)
C6	0.0412 (15)	0.0542 (18)	0.0317 (14)	−0.0138 (13)	−0.0167 (12)	−0.0069 (13)
C7	0.0400 (16)	0.070 (2)	0.0305 (14)	−0.0145 (15)	−0.0100 (13)	−0.0168 (15)
C8	0.0408 (17)	0.080 (2)	0.053 (2)	−0.0002 (16)	−0.0107 (15)	−0.0364 (18)
C9	0.057 (2)	0.067 (2)	0.0493 (19)	0.0056 (16)	−0.0175 (16)	−0.0351 (17)
C10	0.0561 (19)	0.056 (2)	0.057 (2)	0.0106 (15)	−0.0255 (16)	−0.0295 (16)
C11	0.066 (2)	0.0333 (15)	0.0457 (17)	−0.0001 (14)	−0.0289 (16)	−0.0145 (13)
C12	0.0546 (17)	0.0387 (15)	0.0327 (14)	−0.0104 (13)	−0.0201 (13)	−0.0052 (12)
C13	0.074 (2)	0.0514 (19)	0.0453 (18)	−0.0232 (16)	−0.0268 (17)	−0.0083 (15)
C14	0.060 (2)	0.073 (2)	0.0476 (19)	−0.0314 (18)	−0.0198 (17)	−0.0063 (17)
C15	0.0500 (18)	0.074 (2)	0.0412 (17)	−0.0136 (16)	−0.0160 (15)	−0.0095 (16)
C16	0.0530 (18)	0.0515 (18)	0.0388 (16)	−0.0081 (14)	−0.0161 (14)	−0.0124 (14)
C17	0.0480 (16)	0.0388 (15)	0.0277 (13)	−0.0096 (12)	−0.0166 (12)	−0.0036 (11)
O1	0.0574 (12)	0.0413 (11)	0.0281 (10)	−0.0093 (9)	−0.0155 (9)	−0.0099 (8)
O2	0.0470 (11)	0.0442 (11)	0.0349 (10)	−0.0105 (9)	−0.0110 (9)	−0.0173 (9)
O3	0.0514 (12)	0.0668 (14)	0.0488 (12)	0.0087 (10)	−0.0282 (11)	−0.0278 (11)
O4	0.0573 (13)	0.0668 (14)	0.0501 (13)	0.0111 (11)	−0.0320 (11)	−0.0294 (11)
O5	0.0472 (12)	0.0574 (13)	0.0495 (12)	−0.0086 (10)	−0.0220 (10)	−0.0135 (10)
O6	0.088 (3)	0.119 (4)	0.084 (3)	0.033 (3)	−0.061 (3)	−0.060 (3)
O6'	0.083 (9)	0.096 (10)	0.081 (9)	0.016 (7)	−0.052 (7)	−0.032 (7)

Cd1—O1	2.2809 (18)	C6—C7	1.446 (4)
Cd1—O1i	2.2809 (18)	C7—H7A	0.9300
Cd1—O2	2.2799 (18)	C8—C9	1.522 (5)
Cd1—O2i	2.2799 (18)	C8—H8A	0.9700
Cd1—O4i	2.300 (2)	C8—H8B	0.9700
Cd1—O4	2.300 (2)	C9—C10	1.520 (5)
Ni1—O1	2.0098 (19)	C9—H9A	0.9700
Ni1—O2	2.0313 (19)	C9—H9B	0.9700
Ni1—O3	2.080 (2)	C10—H10A	0.9700
Ni1—O5	2.205 (2)	C10—H10B	0.9700
Ni1—N1	2.035 (2)	C11—C12	1.451 (4)
Ni1—N2	2.026 (2)	C11—H11A	0.9300
N1—C7	1.285 (4)	C12—C13	1.403 (4)
N1—C8	1.469 (4)	C12—C17	1.423 (4)
N2—C11	1.271 (4)	C13—C14	1.371 (5)
N2—C10	1.469 (4)	C13—H13A	0.9300
C18—O3	1.228 (4)	C14—C15	1.384 (5)
C18—O4	1.254 (4)	C14—H14A	0.9300
C18—H18	0.9300	C15—C16	1.377 (4)
C1—O1	1.326 (3)	C15—H15A	0.9300
C1—C2	1.394 (4)	C16—C17	1.404 (4)
C1—C6	1.426 (4)	C16—H16A	0.9300
C2—C3	1.391 (4)	C17—O2	1.320 (3)
C2—H2A	0.9300	O5—H5A	0.8500
C3—C4	1.381 (5)	O5—H5B	0.8500
C3—H3A	0.9300	O6—H6A	0.8501
C4—C5	1.365 (5)	O6—H6B	0.8499
C4—H4A	0.9300	O6—H6'B	0.9835
C5—C6	1.401 (4)	O6'—H6'A	0.8500
C5—H5	0.9300	O6'—H6'B	0.8500
O2—Cd1—O2i	180.0	N1—C7—C6	127.5 (3)
O2—Cd1—O1	73.23 (7)	N1—C7—H7A	116.3
O2i—Cd1—O1	106.77 (7)	C6—C7—H7A	116.3
O2—Cd1—O1i	106.77 (7)	N1—C8—C9	113.2 (3)
O2i—Cd1—O1i	73.23 (7)	N1—C8—H8A	108.9
O1—Cd1—O1i	180.0	C9—C8—H8A	108.9
O2—Cd1—O4i	94.86 (7)	N1—C8—H8B	108.9
O2i—Cd1—O4i	85.14 (7)	C9—C8—H8B	108.9
O1—Cd1—O4i	94.24 (7)	H8A—C8—H8B	107.7
O1i—Cd1—O4i	85.76 (7)	C10—C9—C8	113.5 (3)
O2—Cd1—O4	85.14 (7)	C10—C9—H9A	108.9
O2i—Cd1—O4	94.86 (7)	C8—C9—H9A	108.9
O1—Cd1—O4	85.76 (7)	C10—C9—H9B	108.9
O1i—Cd1—O4	94.24 (7)	C8—C9—H9B	108.9
O4i—Cd1—O4	180.0	H9A—C9—H9B	107.7
O1—Ni1—N2	173.13 (9)	N2—C10—C9	111.2 (3)
O1—Ni1—O2	84.62 (8)	N2—C10—H10A	109.4
N2—Ni1—O2	88.57 (9)	C9—C10—H10A	109.4
O1—Ni1—N1	90.47 (9)	N2—C10—H10B	109.4
N2—Ni1—N1	96.25 (10)	C9—C10—H10B	109.4
O2—Ni1—N1	173.51 (9)	H10A—C10—H10B	108.0
O1—Ni1—O3	91.60 (8)	N2—C11—C12	127.0 (3)
N2—Ni1—O3	89.79 (9)	N2—C11—H11A	116.5
O2—Ni1—O3	93.73 (8)	C12—C11—H11A	116.5
N1—Ni1—O3	90.65 (9)	C13—C12—C17	119.2 (3)
O1—Ni1—O5	88.29 (8)	C13—C12—C11	117.6 (3)
N2—Ni1—O5	90.61 (9)	C17—C12—C11	123.2 (3)
O2—Ni1—O5	88.68 (8)	C14—C13—C12	122.1 (3)
N1—Ni1—O5	86.92 (9)	C14—C13—H13A	119.0
O3—Ni1—O5	177.57 (8)	C12—C13—H13A	119.0
C7—N1—C8	117.0 (3)	C13—C14—C15	118.7 (3)
C7—N1—Ni1	122.2 (2)	C13—C14—H14A	120.6
C8—N1—Ni1	120.7 (2)	C15—C14—H14A	120.6
C11—N2—C10	118.3 (3)	C16—C15—C14	121.0 (3)
C11—N2—Ni1	123.6 (2)	C16—C15—H15A	119.5
C10—N2—Ni1	118.0 (2)	C14—C15—H15A	119.5
O3—C18—O4	129.4 (3)	C15—C16—C17	121.5 (3)
O3—C18—H18	115.3	C15—C16—H16A	119.2
O4—C18—H18	115.3	C17—C16—H16A	119.2
O1—C1—C2	120.2 (3)	O2—C17—C16	120.9 (3)
O1—C1—C6	121.7 (3)	O2—C17—C12	121.7 (3)
C2—C1—C6	118.1 (3)	C16—C17—C12	117.4 (3)
C3—C2—C1	121.5 (3)	C1—O1—Ni1	124.49 (17)
C3—C2—H2A	119.2	C1—O1—Cd1	134.11 (18)
C1—C2—H2A	119.2	Ni1—O1—Cd1	98.29 (8)
C4—C3—C2	120.2 (3)	C17—O2—Ni1	123.09 (16)
C4—C3—H3A	119.9	C17—O2—Cd1	135.04 (17)
C2—C3—H3A	119.9	Ni1—O2—Cd1	97.69 (7)
C5—C4—C3	119.2 (3)	C18—O3—Ni1	129.3 (2)
C5—C4—H4A	120.4	C18—O4—Cd1	127.57 (19)
C3—C4—H4A	120.4	Ni1—O5—H5A	103.0
C4—C5—C6	122.6 (3)	Ni1—O5—H5B	115.7
C4—C5—H5	118.7	H5A—O5—H5B	103.2
C6—C5—H5	118.7	H6A—O6—H6B	109.5
C5—C6—C1	118.3 (3)	H6A—O6—H6'B	135.0
C5—C6—C7	117.0 (3)	H6B—O6—H6'B	69.8
C1—C6—C7	124.5 (3)	H6'A—O6'—H6'B	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6′ii	0.85	2.04	2.662 (12)	130
O5—H5B···O6ii	0.85	2.29	2.812 (4)	120
O6—H6B···O4iii	0.85	1.98	2.737 (4)	147
O6′—H6′B···O4iii	0.85	2.19	2.769 (12)	125

Table 1

Selected bond lengths (Å)

Cd1—O1	2.2809 (18)
Cd1—O2	2.2799 (18)
Cd1—O4	2.300 (2)
Ni1—O1	2.0098 (19)
Ni1—O2	2.0313 (19)
Ni1—O3	2.080 (2)
Ni1—O5	2.205 (2)
Ni1—N1	2.035 (2)
Ni1—N2	2.026 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6′i	0.85	2.04	2.662 (12)	130
O5—H5B⋯O6i	0.85	2.29	2.812 (4)	120
O6—H6B⋯O4ii	0.85	1.98	2.737 (4)	147
O6′—H6′B⋯O4ii	0.85	2.19	2.769 (12)	125

Symmetry codes: (i) ; (ii) .