Crystal structures of two nickel compounds comprising neutral Ni^II hydrazone complexes and di­carb­oxy­lic acids

Two Ni^II compounds forming zigzag chain structures through O—H...N hydrogen bonds between di­carb­oxy­lic acids and Ni^II complexes were synthesized, and their structures were determined. They are co-crystals rather than salts.

Key indicators

Structure: 1-Cl

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.053
• wR factor = 0.130
• Data-to-parameter ratio = 15.9

Structure: 1-Br

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.051
• wR factor = 0.107
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Datablock: 1-Cl



Alert level B
PLAT910_ALERT_3_B Missing # of FCF Reflection(s) Below Theta(Min)          11 Note
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW > 10 Outliers ....          4 Check

Alert level C
PLAT155_ALERT_4_C The Triclinic Unitcell is NOT Reduced ..........     Please Do !
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.2 Note
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.969 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         15 Report
PLAT977_ALERT_2_C Check the Negative Difference Density on     H13      -0.46 eA-3
PLAT977_ALERT_2_C Check the Negative Difference Density on     H25      -0.40 eA-3
PLAT977_ALERT_2_C Check the Negative Difference Density on     H26      -0.54 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Note

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details found  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT882_ALERT_1_G Missing datum for _diffrn_reflns_av_unetI/netI .     Please Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         40 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check




Datablock: 1-Br



Alert level B
PLAT910_ALERT_3_B Missing # of FCF Reflection(s) Below Theta(Min)          11 Note

Alert level C
PLAT155_ALERT_4_C The Triclinic Unitcell is NOT Reduced ..........     Please Do !
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.606 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          6 Report
PLAT977_ALERT_2_C Check the Negative Difference Density on     H5C      -0.32 eA-3
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Note

Alert level G
PLAT005_ALERT_5_G No Embedded Refinement Details found  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT434_ALERT_2_G Short Inter HL..HL Contact Br1    ..  Br1     ..       3.52 Ang.
PLAT882_ALERT_1_G Missing datum for _diffrn_reflns_av_unetI/netI .     Please Check
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         13 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2014); cell refinement: CrystalClear (Rigaku, 2014); data reduction: CrystalClear (Rigaku, 2014); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: CrystalStructure (Rigaku, 2014); software used to prepare material for publication: CrystalStructure (Rigaku, 2014).

(1-Cl) Bis{N-[1-(pyridin-2-yl-κN)ethylidene]pyridine-4-carbohydrazonato-κ²N',O}nickel(II)–2,5-dichloroterephthalic acid (1/1)

Crystal data

[Ni(C13H11N4O)2](C8H4Cl2O4)	Z = 2
Mr = 772.24	F(000) = 792.00
Triclinic, P1	Dx = 1.587 Mg m^−3
a = 7.9596 (18) Å	Mo Kα radiation, λ = 0.71075 Å
b = 8.7600 (17) Å	Cell parameters from 5812 reflections
c = 24.121 (4) Å	θ = 1.8–30.7°
α = 76.138 (8)°	µ = 0.83 mm^−1
β = 81.803 (8)°	T = 123 K
γ = 87.253 (9)°	Plate, brown
V = 1616.0 (6) Å^3	0.02 × 0.02 × 0.01 mm

Data collection

Rigaku Saturn724 diffractometer	6814 reflections with F^2 > 2.0σ(F^2)
Detector resolution: 14.222 pixels mm^-1	Rint = 0.044
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −10→10
Tmin = 0.761, Tmax = 0.848	k = −11→11
27850 measured reflections	l = −31→31
7359 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 1.4269P] where P = (Fo^2 + 2Fc^2)/3
7359 reflections	(Δ/σ)max = 0.001
464 parameters	Δρmax = 0.57 e Å^−3
0 restraints	Δρmin = −0.92 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.67086 (4)	0.43172 (3)	0.25224 (2)	0.01854 (10)
Cl1	0.41155 (8)	−0.35525 (7)	0.03245 (3)	0.02750 (15)
Cl2	0.79694 (9)	−0.13848 (8)	0.62117 (3)	0.03312 (17)
O1	0.7541 (2)	0.2053 (2)	0.28890 (7)	0.0231 (4)
O2	0.4392 (2)	0.3451 (2)	0.24024 (7)	0.0216 (4)
O3	0.8331 (3)	0.3969 (2)	0.48427 (8)	0.0337 (5)
O4	1.0219 (3)	0.4091 (2)	0.40572 (9)	0.0391 (5)
O5	0.7989 (2)	0.0224 (2)	0.09773 (8)	0.0285 (4)
O6	0.9030 (3)	0.1760 (3)	0.01231 (8)	0.0330 (4)
N1	0.5819 (3)	0.6608 (2)	0.25437 (9)	0.0197 (4)
N2	0.6092 (3)	0.4157 (2)	0.33633 (8)	0.0188 (4)
N3	0.6286 (3)	0.2722 (2)	0.37388 (9)	0.0212 (4)
N4	0.7897 (3)	−0.2955 (3)	0.43917 (10)	0.0298 (5)
N5	0.9154 (3)	0.5276 (3)	0.22513 (9)	0.0210 (4)
N6	0.7008 (3)	0.4439 (2)	0.16820 (8)	0.0184 (4)
N7	0.5775 (3)	0.3818 (2)	0.14568 (8)	0.0198 (4)
N8	0.0405 (3)	0.1303 (3)	0.13524 (9)	0.0236 (4)
C1	0.5204 (3)	0.6749 (3)	0.30831 (10)	0.0187 (5)
C2	0.4620 (3)	0.8194 (3)	0.31865 (11)	0.0216 (5)
C3	0.4758 (3)	0.9523 (3)	0.27352 (11)	0.0253 (5)
C4	0.5456 (3)	0.9378 (3)	0.21886 (11)	0.0243 (5)
C5	0.5948 (3)	0.7898 (3)	0.21134 (10)	0.0224 (5)
C6	0.5269 (3)	0.5291 (3)	0.35434 (10)	0.0197 (5)
C7	0.4446 (4)	0.5154 (3)	0.41466 (11)	0.0292 (6)
C8	0.7073 (3)	0.1748 (3)	0.34310 (10)	0.0199 (5)
C9	0.7388 (3)	0.0127 (3)	0.37742 (10)	0.0214 (5)
C10	0.6540 (4)	−0.0432 (3)	0.43257 (11)	0.0277 (6)
C11	0.6816 (4)	−0.1960 (3)	0.46184 (12)	0.0322 (6)
C12	0.8510 (4)	−0.0892 (3)	0.35420 (11)	0.0256 (5)
C13	0.8734 (4)	−0.2401 (3)	0.38644 (11)	0.0285 (6)
C14	0.9496 (3)	0.5711 (3)	0.16687 (10)	0.0209 (5)
C15	1.0827 (3)	0.6692 (3)	0.13930 (12)	0.0292 (6)
C16	1.1852 (4)	0.7223 (4)	0.17243 (13)	0.0368 (7)
C17	1.1539 (4)	0.6737 (4)	0.23198 (13)	0.0364 (7)
C18	1.0174 (3)	0.5764 (3)	0.25663 (12)	0.0272 (5)
C19	0.8334 (3)	0.5091 (3)	0.13497 (10)	0.0195 (5)
C20	0.8694 (3)	0.5198 (3)	0.07165 (10)	0.0250 (5)
C21	0.4492 (3)	0.3366 (3)	0.18769 (10)	0.0195 (5)
C22	0.3055 (3)	0.2660 (3)	0.16921 (10)	0.0202 (5)
C23	0.3146 (3)	0.2441 (3)	0.11342 (11)	0.0243 (5)
C24	0.1815 (3)	0.1762 (3)	0.09809 (11)	0.0266 (5)
C25	0.1580 (3)	0.2183 (3)	0.20755 (10)	0.0208 (5)
C26	0.0296 (3)	0.1524 (3)	0.18879 (11)	0.0234 (5)
C27	0.7947 (3)	0.0902 (3)	0.04348 (11)	0.0232 (5)
C28	0.6401 (3)	0.0472 (3)	0.02141 (10)	0.0215 (5)
C29	0.5893 (3)	−0.1087 (3)	0.03644 (10)	0.0221 (5)
C30	0.4537 (3)	−0.1554 (3)	0.01532 (10)	0.0207 (5)
C31	0.9135 (3)	−0.0673 (3)	0.55392 (11)	0.0236 (5)
C32	0.8909 (3)	0.0907 (3)	0.52835 (11)	0.0242 (5)
C33	0.9751 (3)	0.1619 (3)	0.47446 (11)	0.0226 (5)
C34	0.9472 (3)	0.3356 (3)	0.45046 (11)	0.0249 (5)
H1	0.41316	0.82673	0.35624	0.0260*
H2	0.43799	1.05195	0.27992	0.0303*
H3	0.55916	1.02732	0.1874	0.0291*
H4	0.64003	0.7793	0.17378	0.0269*
H5B	0.51437	0.44762	0.44126	0.0351*
H6C	0.3319	0.46964	0.41959	0.0351*
H7A	0.4332	0.61998	0.42288	0.0351*
H8	0.5774	0.02358	0.45005	0.0333*
H9	0.62211	−0.23263	0.49945	0.0386*
H10	0.91159	−0.05553	0.31661	0.0307*
H11	0.95218	−0.30803	0.37036	0.0342*
H12	1.10347	0.69948	0.09841	0.0351*
H13	1.27605	0.79128	0.1545	0.0442*
H14	1.22456	0.70646	0.25544	0.0437*
H15	0.99564	0.54319	0.29744	0.0326*
H16C	0.96065	0.44528	0.06411	0.0299*
H17A	0.90443	0.62684	0.05154	0.0299*
H18B	0.76681	0.49436	0.05776	0.0299*
H19	0.41227	0.27593	0.08615	0.0291*
H20	0.18943	0.16126	0.06006	0.0319*
H21	0.14673	0.23126	0.24591	0.0250*
H22	−0.07078	0.12132	0.21482	0.0280*
H23	0.64945	−0.18442	0.06181	0.0265*
H24	0.81501	0.15245	0.54843	0.0290*
H25	0.82374	0.49396	0.4703	0.0404*
H26	0.882	0.05571	0.10908	0.0341*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02329 (18)	0.01591 (17)	0.01524 (16)	0.00197 (12)	−0.00110 (12)	−0.00266 (12)
Cl1	0.0335 (3)	0.0171 (3)	0.0299 (3)	−0.0019 (2)	−0.0009 (3)	−0.0035 (2)
Cl2	0.0421 (4)	0.0239 (3)	0.0274 (3)	0.0045 (3)	0.0084 (3)	−0.0030 (3)
O1	0.0305 (10)	0.0197 (9)	0.0174 (8)	0.0048 (7)	−0.0001 (7)	−0.0036 (7)
O2	0.0253 (9)	0.0213 (9)	0.0182 (8)	−0.0013 (7)	−0.0008 (7)	−0.0058 (7)
O3	0.0475 (12)	0.0179 (9)	0.0294 (10)	0.0098 (9)	0.0061 (9)	−0.0019 (8)
O4	0.0489 (13)	0.0232 (10)	0.0352 (11)	0.0071 (9)	0.0109 (10)	0.0015 (9)
O5	0.0267 (10)	0.0383 (11)	0.0188 (9)	−0.0092 (8)	−0.0055 (7)	−0.0004 (8)
O6	0.0336 (11)	0.0384 (11)	0.0238 (10)	−0.0130 (9)	−0.0042 (8)	0.0018 (8)
N1	0.0221 (10)	0.0177 (10)	0.0185 (10)	0.0029 (8)	−0.0025 (8)	−0.0036 (8)
N2	0.0218 (10)	0.0165 (10)	0.0170 (9)	0.0001 (8)	−0.0014 (8)	−0.0024 (8)
N3	0.0280 (11)	0.0166 (10)	0.0171 (10)	0.0016 (8)	−0.0025 (8)	−0.0008 (8)
N4	0.0436 (14)	0.0178 (11)	0.0263 (12)	0.0037 (10)	−0.0066 (10)	−0.0019 (9)
N5	0.0213 (10)	0.0217 (10)	0.0198 (10)	0.0039 (8)	−0.0032 (8)	−0.0050 (8)
N6	0.0214 (10)	0.0158 (10)	0.0175 (9)	0.0018 (8)	−0.0030 (8)	−0.0030 (8)
N7	0.0226 (10)	0.0201 (10)	0.0167 (9)	−0.0011 (8)	−0.0024 (8)	−0.0041 (8)
N8	0.0235 (11)	0.0242 (11)	0.0214 (10)	−0.0001 (9)	−0.0030 (8)	−0.0023 (9)
C1	0.0165 (11)	0.0194 (11)	0.0195 (11)	−0.0006 (9)	−0.0028 (9)	−0.0033 (9)
C2	0.0271 (13)	0.0169 (11)	0.0199 (12)	0.0008 (9)	−0.0006 (9)	−0.0039 (9)
C3	0.0279 (13)	0.0200 (12)	0.0288 (13)	0.0041 (10)	−0.0052 (10)	−0.0074 (10)
C4	0.0295 (13)	0.0168 (12)	0.0230 (12)	0.0028 (10)	−0.0020 (10)	0.0008 (10)
C5	0.0233 (12)	0.0228 (12)	0.0179 (11)	0.0028 (10)	−0.0017 (9)	0.0002 (9)
C6	0.0210 (12)	0.0186 (12)	0.0183 (11)	−0.0004 (9)	−0.0001 (9)	−0.0032 (9)
C7	0.0407 (16)	0.0206 (13)	0.0214 (13)	0.0037 (11)	0.0061 (11)	−0.0020 (10)
C8	0.0220 (12)	0.0180 (12)	0.0184 (11)	0.0013 (9)	−0.0036 (9)	−0.0014 (9)
C9	0.0263 (13)	0.0179 (12)	0.0193 (12)	0.0020 (10)	−0.0051 (9)	−0.0025 (9)
C10	0.0352 (15)	0.0224 (13)	0.0220 (12)	0.0033 (11)	0.0016 (11)	−0.0022 (10)
C11	0.0437 (17)	0.0218 (13)	0.0241 (13)	0.0044 (12)	0.0028 (12)	0.0028 (11)
C12	0.0323 (14)	0.0221 (13)	0.0216 (12)	0.0038 (10)	−0.0032 (10)	−0.0049 (10)
C13	0.0389 (15)	0.0209 (13)	0.0257 (13)	0.0081 (11)	−0.0044 (11)	−0.0071 (10)
C14	0.0196 (12)	0.0210 (12)	0.0212 (12)	0.0054 (9)	−0.0015 (9)	−0.0050 (9)
C15	0.0244 (13)	0.0356 (15)	0.0259 (13)	−0.0007 (11)	−0.0022 (10)	−0.0043 (11)
C16	0.0245 (14)	0.0495 (19)	0.0356 (16)	−0.0112 (13)	−0.0011 (12)	−0.0080 (14)
C17	0.0266 (14)	0.0505 (19)	0.0354 (16)	−0.0052 (13)	−0.0077 (12)	−0.0136 (14)
C18	0.0252 (13)	0.0338 (14)	0.0232 (13)	0.0030 (11)	−0.0050 (10)	−0.0078 (11)
C19	0.0210 (12)	0.0171 (11)	0.0176 (11)	0.0029 (9)	−0.0006 (9)	−0.0004 (9)
C20	0.0284 (13)	0.0268 (13)	0.0176 (12)	−0.0020 (10)	0.0019 (10)	−0.0037 (10)
C21	0.0250 (12)	0.0138 (11)	0.0180 (11)	0.0051 (9)	−0.0034 (9)	−0.0015 (9)
C22	0.0244 (12)	0.0131 (11)	0.0216 (12)	0.0053 (9)	−0.0033 (9)	−0.0021 (9)
C23	0.0233 (12)	0.0298 (14)	0.0192 (12)	0.0008 (10)	0.0007 (9)	−0.0069 (10)
C24	0.0276 (13)	0.0346 (14)	0.0184 (12)	−0.0004 (11)	−0.0010 (10)	−0.0092 (11)
C25	0.0231 (12)	0.0199 (12)	0.0184 (11)	0.0019 (9)	−0.0007 (9)	−0.0039 (9)
C26	0.0247 (13)	0.0235 (13)	0.0206 (12)	0.0024 (10)	−0.0015 (9)	−0.0040 (10)
C27	0.0269 (13)	0.0217 (12)	0.0202 (12)	−0.0004 (10)	−0.0016 (10)	−0.0044 (10)
C28	0.0228 (12)	0.0232 (12)	0.0176 (11)	0.0002 (10)	0.0004 (9)	−0.0048 (9)
C29	0.0273 (13)	0.0187 (12)	0.0187 (11)	0.0031 (10)	−0.0027 (9)	−0.0020 (9)
C30	0.0264 (12)	0.0182 (11)	0.0168 (11)	0.0001 (9)	−0.0012 (9)	−0.0039 (9)
C31	0.0267 (13)	0.0224 (12)	0.0205 (12)	0.0024 (10)	−0.0006 (10)	−0.0051 (10)
C32	0.0268 (13)	0.0212 (12)	0.0254 (13)	0.0034 (10)	−0.0019 (10)	−0.0089 (10)
C33	0.0246 (13)	0.0197 (12)	0.0242 (12)	0.0013 (10)	−0.0051 (10)	−0.0054 (10)
C34	0.0305 (14)	0.0179 (12)	0.0255 (13)	0.0041 (10)	−0.0029 (10)	−0.0050 (10)

Geometric parameters (Å, º)

Ni1—O1	2.0870 (17)	C16—C17	1.386 (4)
Ni1—O2	2.1099 (19)	C17—C18	1.386 (4)
Ni1—N1	2.106 (2)	C19—C20	1.494 (3)
Ni1—N2	1.990 (2)	C21—C22	1.495 (4)
Ni1—N5	2.110 (2)	C22—C23	1.396 (4)
Ni1—N6	1.985 (2)	C22—C25	1.400 (3)
Cl1—C30	1.738 (3)	C23—C24	1.374 (4)
Cl2—C31	1.739 (2)	C25—C26	1.377 (4)
O1—C8	1.274 (3)	C27—C28	1.506 (4)
O2—C21	1.278 (3)	C28—C29	1.391 (4)
C34—O3	1.316 (3)	C28—C30^i	1.400 (3)
C34—O4	1.206 (3)	C29—C30	1.375 (4)
C27—O5	1.306 (3)	C31—C32	1.388 (3)
C27—O6	1.216 (3)	C31—C33^ii	1.404 (4)
N1—C1	1.355 (3)	C32—C33	1.390 (3)
N1—C5	1.335 (3)	C33—C34	1.510 (3)
N2—N3	1.379 (3)	O3—H25	0.840
N2—C6	1.292 (3)	O5—H26	0.840
N3—C8	1.338 (3)	C2—H1	0.950
N4—C11	1.350 (4)	C3—H2	0.950
N4—C13	1.338 (3)	C4—H3	0.950
N5—C14	1.356 (3)	C5—H4	0.950
N5—C18	1.336 (4)	C7—H5B	0.980
N6—N7	1.378 (3)	C7—H6C	0.980
N6—C19	1.296 (3)	C7—H7A	0.980
N7—C21	1.333 (3)	C10—H8	0.950
N8—C24	1.345 (3)	C11—H9	0.950
N8—C26	1.342 (4)	C12—H10	0.950
C1—C2	1.393 (4)	C13—H11	0.950
C1—C6	1.482 (3)	C15—H12	0.950
C2—C3	1.387 (3)	C16—H13	0.950
C3—C4	1.389 (4)	C17—H14	0.950
C4—C5	1.382 (4)	C18—H15	0.950
C6—C7	1.488 (3)	C20—H16C	0.980
C8—C9	1.492 (3)	C20—H17A	0.980
C9—C10	1.389 (3)	C20—H18B	0.980
C9—C12	1.389 (4)	C23—H19	0.950
C10—C11	1.379 (4)	C24—H20	0.950
C12—C13	1.382 (3)	C25—H21	0.950
C14—C15	1.384 (3)	C26—H22	0.950
C14—C19	1.481 (4)	C29—H23	0.950
C15—C16	1.386 (5)	C32—H24	0.950
O1—Ni1—O2	91.34 (7)	N8—C26—C25	122.6 (2)
O1—Ni1—N1	154.21 (8)	O5—C27—O6	125.6 (3)
O1—Ni1—N2	77.13 (8)	O5—C27—C28	112.6 (2)
O1—Ni1—N5	95.75 (8)	O6—C27—C28	121.8 (2)
O1—Ni1—N6	104.55 (8)	C27—C28—C29	119.0 (2)
O2—Ni1—N1	96.67 (8)	C27—C28—C30^i	123.5 (2)
O2—Ni1—N2	95.71 (8)	C29—C28—C30^i	117.5 (2)
O2—Ni1—N5	154.86 (8)	C28—C29—C30	121.3 (2)
O2—Ni1—N6	77.12 (8)	Cl1—C30—C28^i	121.3 (2)
N1—Ni1—N2	77.70 (8)	Cl1—C30—C29	117.39 (18)
N1—Ni1—N5	87.32 (8)	C28^i—C30—C29	121.2 (2)
N1—Ni1—N6	101.13 (8)	Cl2—C31—C32	116.7 (2)
N2—Ni1—N5	109.38 (9)	Cl2—C31—C33^ii	123.01 (18)
N2—Ni1—N6	172.61 (9)	C32—C31—C33^ii	120.3 (2)
N5—Ni1—N6	77.75 (9)	C31—C32—C33	122.4 (2)
Ni1—O1—C8	108.99 (15)	C31^ii—C33—C32	117.2 (2)
Ni1—O2—C21	108.26 (15)	C31^ii—C33—C34	123.7 (2)
Ni1—N1—C1	112.70 (15)	C32—C33—C34	119.1 (2)
Ni1—N1—C5	128.03 (18)	O3—C34—O4	124.2 (2)
C1—N1—C5	118.9 (2)	O3—C34—C33	112.1 (2)
Ni1—N2—N3	118.43 (16)	O4—C34—C33	123.7 (2)
Ni1—N2—C6	120.19 (15)	C34—O3—H25	109.478
N3—N2—C6	120.36 (19)	C27—O5—H26	109.477
N2—N3—C8	107.53 (19)	C1—C2—H1	120.325
C11—N4—C13	117.4 (2)	C3—C2—H1	120.322
Ni1—N5—C14	111.70 (17)	C2—C3—H2	120.450
Ni1—N5—C18	128.02 (17)	C4—C3—H2	120.447
C14—N5—C18	118.7 (2)	C3—C4—H3	120.816
Ni1—N6—N7	118.72 (13)	C5—C4—H3	120.812
Ni1—N6—C19	120.82 (19)	N1—C5—H4	118.447
N7—N6—C19	120.5 (2)	C4—C5—H4	118.448
N6—N7—C21	108.0 (2)	C6—C7—H5B	109.470
C24—N8—C26	118.8 (2)	C6—C7—H6C	109.478
N1—C1—C2	121.0 (2)	C6—C7—H7A	109.475
N1—C1—C6	115.3 (2)	H5B—C7—H6C	109.469
C2—C1—C6	123.6 (2)	H5B—C7—H7A	109.464
C1—C2—C3	119.4 (2)	H6C—C7—H7A	109.472
C2—C3—C4	119.1 (2)	C9—C10—H8	120.135
C3—C4—C5	118.4 (2)	C11—C10—H8	120.151
N1—C5—C4	123.1 (2)	N4—C11—H9	118.708
N2—C6—C1	113.0 (2)	C10—C11—H9	118.699
N2—C6—C7	123.9 (2)	C9—C12—H10	120.404
C1—C6—C7	123.1 (2)	C13—C12—H10	120.405
O1—C8—N3	127.3 (2)	N4—C13—H11	118.362
O1—C8—C9	118.1 (2)	C12—C13—H11	118.358
N3—C8—C9	114.6 (2)	C14—C15—H12	120.607
C8—C9—C10	121.6 (2)	C16—C15—H12	120.613
C8—C9—C12	120.6 (2)	C15—C16—H13	120.324
C10—C9—C12	117.8 (2)	C17—C16—H13	120.330
C9—C10—C11	119.7 (3)	C16—C17—H14	120.669
N4—C11—C10	122.6 (2)	C18—C17—H14	120.655
C9—C12—C13	119.2 (2)	N5—C18—H15	118.782
N4—C13—C12	123.3 (3)	C17—C18—H15	118.778
N5—C14—C15	122.0 (3)	C19—C20—H16C	109.476
N5—C14—C19	115.6 (2)	C19—C20—H17A	109.482
C15—C14—C19	122.5 (2)	C19—C20—H18B	109.472
C14—C15—C16	118.8 (3)	H16C—C20—H17A	109.466
C15—C16—C17	119.3 (3)	H16C—C20—H18B	109.468
C16—C17—C18	118.7 (3)	H17A—C20—H18B	109.463
N5—C18—C17	122.4 (3)	C22—C23—H19	120.140
N6—C19—C14	112.5 (2)	C24—C23—H19	120.125
N6—C19—C20	124.7 (2)	N8—C24—H20	118.975
C14—C19—C20	122.8 (2)	C23—C24—H20	118.982
O2—C21—N7	127.5 (2)	C22—C25—H21	120.510
O2—C21—C22	118.7 (2)	C26—C25—H21	120.521
N7—C21—C22	113.8 (2)	N8—C26—H22	118.675
C21—C22—C23	121.1 (2)	C25—C26—H22	118.677
C21—C22—C25	121.0 (2)	C28—C29—H23	119.339
C23—C22—C25	117.8 (2)	C30—C29—H23	119.342
C22—C23—C24	119.7 (2)	C31—C32—H24	118.785
N8—C24—C23	122.0 (3)	C33—C32—H24	118.786
C22—C25—C26	119.0 (2)
O1—Ni1—O2—C21	−99.87 (11)	Ni1—N6—N7—C21	5.8 (2)
O2—Ni1—O1—C8	−89.54 (12)	Ni1—N6—C19—C14	−0.9 (3)
O1—Ni1—N1—C1	−17.2 (3)	Ni1—N6—C19—C20	178.20 (13)
O1—Ni1—N1—C5	155.73 (14)	N7—N6—C19—C14	178.99 (17)
N1—Ni1—O1—C8	18.9 (3)	N7—N6—C19—C20	−1.9 (3)
O1—Ni1—N2—N3	−7.52 (13)	C19—N6—N7—C21	−174.06 (19)
O1—Ni1—N2—C6	−176.01 (17)	N6—N7—C21—O2	−1.1 (3)
N2—Ni1—O1—C8	6.01 (12)	N6—N7—C21—C22	−179.84 (16)
O1—Ni1—N5—C14	114.34 (13)	C24—N8—C26—C25	−0.9 (3)
O1—Ni1—N5—C18	−80.17 (17)	C26—N8—C24—C23	0.4 (4)
N5—Ni1—O1—C8	114.62 (13)	N1—C1—C2—C3	−3.6 (4)
O1—Ni1—N6—N7	82.01 (14)	N1—C1—C6—N2	7.8 (3)
O1—Ni1—N6—C19	−98.13 (14)	N1—C1—C6—C7	−171.4 (2)
N6—Ni1—O1—C8	−166.58 (12)	C2—C1—C6—N2	−169.9 (2)
O2—Ni1—N1—C1	90.00 (14)	C2—C1—C6—C7	10.9 (4)
O2—Ni1—N1—C5	−97.03 (17)	C6—C1—C2—C3	173.9 (2)
N1—Ni1—O2—C21	104.69 (11)	C1—C2—C3—C4	0.9 (4)
O2—Ni1—N2—N3	82.55 (14)	C2—C3—C4—C5	1.6 (4)
O2—Ni1—N2—C6	−85.94 (16)	C3—C4—C5—N1	−1.5 (4)
N2—Ni1—O2—C21	−177.07 (11)	O1—C8—C9—C10	−162.4 (2)
O2—Ni1—N5—C14	8.7 (3)	O1—C8—C9—C12	15.5 (4)
O2—Ni1—N5—C18	174.18 (12)	N3—C8—C9—C10	16.5 (4)
N5—Ni1—O2—C21	6.7 (2)	N3—C8—C9—C12	−165.5 (2)
O2—Ni1—N6—N7	−6.01 (12)	C8—C9—C10—C11	177.2 (2)
O2—Ni1—N6—C19	173.85 (16)	C8—C9—C12—C13	−178.0 (2)
N6—Ni1—O2—C21	4.75 (10)	C10—C9—C12—C13	0.0 (4)
N1—Ni1—N2—N3	178.16 (16)	C12—C9—C10—C11	−0.8 (4)
N1—Ni1—N2—C6	9.67 (15)	C9—C10—C11—N4	0.4 (5)
N2—Ni1—N1—C1	−4.42 (13)	C9—C12—C13—N4	1.2 (5)
N2—Ni1—N1—C5	168.55 (19)	N5—C14—C15—C16	0.9 (4)
N1—Ni1—N5—C14	−91.35 (14)	N5—C14—C19—N6	10.7 (3)
N1—Ni1—N5—C18	74.15 (17)	N5—C14—C19—C20	−168.44 (19)
N5—Ni1—N1—C1	−114.92 (14)	C15—C14—C19—N6	−168.3 (2)
N5—Ni1—N1—C5	58.05 (18)	C15—C14—C19—C20	12.6 (4)
N1—Ni1—N6—N7	−100.40 (14)	C19—C14—C15—C16	179.8 (2)
N1—Ni1—N6—C19	79.46 (15)	C14—C15—C16—C17	1.2 (4)
N6—Ni1—N1—C1	168.12 (13)	C15—C16—C17—C18	−1.7 (5)
N6—Ni1—N1—C5	−18.91 (19)	C16—C17—C18—N5	0.1 (4)
N2—Ni1—N5—C14	−167.31 (12)	O2—C21—C22—C23	−175.62 (18)
N2—Ni1—N5—C18	−1.82 (19)	O2—C21—C22—C25	3.7 (3)
N5—Ni1—N2—N3	−99.16 (15)	N7—C21—C22—C23	3.2 (3)
N5—Ni1—N2—C6	92.36 (16)	N7—C21—C22—C25	−177.40 (18)
N5—Ni1—N6—N7	174.84 (15)	C21—C22—C23—C24	178.79 (19)
N5—Ni1—N6—C19	−5.30 (14)	C21—C22—C25—C26	−179.32 (18)
N6—Ni1—N5—C14	10.66 (13)	C23—C22—C25—C26	0.0 (3)
N6—Ni1—N5—C18	176.15 (18)	C25—C22—C23—C24	−0.6 (3)
Ni1—O1—C8—N3	−4.5 (3)	C22—C23—C24—N8	0.4 (4)
Ni1—O1—C8—C9	174.20 (14)	C22—C25—C26—N8	0.7 (4)
Ni1—O2—C21—N7	−3.5 (3)	O5—C27—C28—C29	−43.4 (3)
Ni1—O2—C21—C22	175.16 (13)	O5—C27—C28—C30^i	138.8 (2)
Ni1—N1—C1—C2	177.44 (15)	O6—C27—C28—C29	134.9 (2)
Ni1—N1—C1—C6	−0.3 (2)	O6—C27—C28—C30^i	−43.0 (4)
Ni1—N1—C5—C4	−173.77 (15)	C27—C28—C29—C30	−177.0 (2)
C1—N1—C5—C4	−1.2 (4)	C27—C28—C30^i—Cl1^i	−7.1 (3)
C5—N1—C1—C2	3.8 (3)	C27—C28—C30^i—C29^i	176.9 (2)
C5—N1—C1—C6	−173.9 (2)	C29—C28—C30^i—Cl1^i	175.04 (18)
Ni1—N2—N3—C8	7.2 (2)	C29—C28—C30^i—C29^i	−1.0 (3)
Ni1—N2—C6—C1	−12.4 (3)	C30^i—C28—C29—C30	1.0 (3)
Ni1—N2—C6—C7	166.82 (15)	C28—C29—C30—Cl1	175.15 (19)
N3—N2—C6—C1	179.38 (19)	C28—C29—C30—C28^i	−1.0 (4)
N3—N2—C6—C7	−1.4 (4)	Cl2—C31—C32—C33	−179.38 (18)
C6—N2—N3—C8	175.6 (2)	Cl2—C31—C33^ii—C32^ii	179.35 (18)
N2—N3—C8—O1	−1.3 (4)	Cl2—C31—C33^ii—C34^ii	1.3 (4)
N2—N3—C8—C9	179.92 (18)	C32—C31—C33^ii—C32^ii	−0.1 (4)
C11—N4—C13—C12	−1.7 (4)	C32—C31—C33^ii—C34^ii	−178.2 (2)
C13—N4—C11—C10	0.9 (4)	C33^ii—C31—C32—C33	0.1 (4)
Ni1—N5—C14—C15	164.49 (15)	C31—C32—C33—C31^ii	−0.1 (4)
Ni1—N5—C14—C19	−14.5 (2)	C31—C32—C33—C34	−178.3 (2)
Ni1—N5—C18—C17	−162.65 (15)	C31^ii—C33—C34—O3	178.1 (2)
C14—N5—C18—C17	2.0 (4)	C31^ii—C33—C34—O4	−2.4 (5)
C18—N5—C14—C15	−2.5 (3)	C32—C33—C34—O3	−3.9 (4)
C18—N5—C14—C19	178.5 (2)	C32—C33—C34—O4	175.6 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H25···N4^iii	0.84	1.84	2.679 (3)	177
O5—H26···N8^iv	0.84	1.71	2.547 (3)	176

Symmetry codes: (iii) x, y+1, z; (iv) x+1, y, z.

(1-Br) Bis{N-[1-(pyridin-2-yl-κN)ethylidene]pyridine-4-carbohydrazonato-κ²N',O}nickel(II)–2,5-dibromoterephthalic acid (1/1)

Crystal data

[Ni(C13H11N4O)2](C8H4Br2O4)	Z = 2
Mr = 861.14	F(000) = 864.00
Triclinic, P1	Dx = 1.747 Mg m^−3
a = 7.8740 (14) Å	Mo Kα radiation, λ = 0.71075 Å
b = 8.9716 (15) Å	Cell parameters from 6236 reflections
c = 24.233 (4) Å	θ = 1.8–30.8°
α = 75.040 (9)°	µ = 3.10 mm^−1
β = 82.162 (10)°	T = 123 K
γ = 86.007 (11)°	Plate, brown
V = 1637.3 (5) Å^3	0.02 × 0.02 × 0.01 mm

Data collection

Rigaku Saturn724 diffractometer	6665 reflections with F^2 > 2.0σ(F^2)
Detector resolution: 14.222 pixels mm^-1	Rint = 0.050
ω scans	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −10→10
Tmin = 0.467, Tmax = 0.538	k = −11→11
28760 measured reflections	l = −31→31
7439 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.036P)^2 + 2.3422P] where P = (Fo^2 + 2Fc^2)/3
7439 reflections	(Δ/σ)max = 0.001
464 parameters	Δρmax = 0.72 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.08134 (5)	0.36721 (4)	0.45974 (2)	0.03504 (11)
Br2	0.71262 (5)	0.14742 (4)	0.87301 (2)	0.02901 (11)
Ni1	0.17274 (6)	0.41976 (5)	0.75363 (2)	0.02102 (11)
O1	0.2587 (3)	0.1969 (3)	0.79096 (10)	0.0250 (5)
O2	−0.0585 (3)	0.3334 (3)	0.74089 (9)	0.0236 (5)
O3	0.3310 (4)	0.3923 (3)	0.98699 (11)	0.0321 (6)
O4	0.5246 (4)	0.4085 (3)	0.90949 (12)	0.0394 (7)
O5	0.3029 (3)	0.0259 (3)	0.59558 (10)	0.0335 (6)
O6	0.4060 (4)	0.1768 (3)	0.50971 (11)	0.0392 (7)
N1	0.0800 (4)	0.6459 (3)	0.75401 (12)	0.0219 (6)
N2	0.1146 (4)	0.4059 (3)	0.83712 (11)	0.0198 (6)
N3	0.1365 (4)	0.2643 (3)	0.87523 (11)	0.0206 (6)
N4	0.2905 (4)	−0.3001 (3)	0.94192 (13)	0.0280 (7)
N5	0.4171 (4)	0.5170 (3)	0.72801 (12)	0.0230 (6)
N6	0.2067 (4)	0.4314 (3)	0.67004 (11)	0.0207 (6)
N7	0.0867 (4)	0.3661 (3)	0.64776 (11)	0.0226 (6)
N8	−0.4536 (4)	0.1265 (3)	0.63430 (12)	0.0262 (6)
C1	0.0264 (4)	0.6627 (4)	0.80766 (14)	0.0201 (7)
C2	−0.0243 (5)	0.8064 (4)	0.81732 (15)	0.0250 (7)
C3	−0.0113 (5)	0.9368 (4)	0.77106 (15)	0.0278 (8)
C4	0.0499 (5)	0.9204 (4)	0.71676 (15)	0.0281 (8)
C5	0.0911 (5)	0.7722 (4)	0.70999 (15)	0.0264 (8)
C6	0.0339 (4)	0.5190 (4)	0.85436 (14)	0.0210 (7)
C7	−0.0436 (5)	0.5096 (4)	0.91452 (14)	0.0275 (8)
C8	0.2134 (4)	0.1678 (4)	0.84499 (14)	0.0211 (7)
C9	0.2437 (4)	0.0059 (4)	0.87960 (14)	0.0210 (7)
C10	0.1563 (5)	−0.0480 (4)	0.93437 (15)	0.0277 (8)
C11	0.1833 (5)	−0.2009 (4)	0.96349 (16)	0.0308 (8)
C12	0.3547 (5)	−0.0961 (4)	0.85712 (15)	0.0260 (7)
C13	0.3756 (5)	−0.2461 (4)	0.88957 (15)	0.0275 (8)
C14	0.4490 (4)	0.5644 (4)	0.66952 (14)	0.0234 (7)
C15	0.5748 (5)	0.6703 (4)	0.64261 (16)	0.0303 (8)
C16	0.6693 (5)	0.7273 (5)	0.67645 (18)	0.0394 (10)
C17	0.6416 (5)	0.6749 (5)	0.73531 (17)	0.0366 (9)
C18	0.5135 (5)	0.5698 (4)	0.75984 (16)	0.0291 (8)
C19	0.3388 (4)	0.4983 (4)	0.63754 (14)	0.0221 (7)
C20	0.3813 (5)	0.5089 (4)	0.57493 (14)	0.0291 (8)
C21	−0.0439 (5)	0.3231 (4)	0.68878 (14)	0.0224 (7)
C22	−0.1881 (4)	0.2546 (4)	0.66969 (14)	0.0216 (7)
C23	−0.1743 (5)	0.2322 (4)	0.61435 (15)	0.0266 (8)
C24	−0.3091 (5)	0.1685 (4)	0.59875 (15)	0.0298 (8)
C25	−0.3379 (5)	0.2111 (4)	0.70672 (14)	0.0233 (7)
C26	−0.4671 (5)	0.1476 (4)	0.68768 (15)	0.0263 (7)
C27	0.2984 (5)	0.0920 (4)	0.54129 (15)	0.0285 (8)
C28	0.1417 (5)	0.0496 (4)	0.51998 (14)	0.0244 (7)
C29	0.0942 (5)	−0.1046 (4)	0.53744 (15)	0.0267 (8)
C30	0.0450 (5)	0.1528 (4)	0.48204 (14)	0.0244 (7)
C31	0.5852 (4)	0.0696 (4)	0.94649 (14)	0.0220 (7)
C32	0.3907 (5)	0.0870 (4)	1.02952 (14)	0.0238 (7)
C33	0.4753 (4)	0.1608 (4)	0.97543 (14)	0.0221 (7)
C34	0.4474 (5)	0.3329 (4)	0.95307 (15)	0.0250 (7)
H1	−0.06715	0.8156	0.85493	0.0299*
H2	−0.0442	1.03605	0.77688	0.0333*
H3	0.06352	1.00786	0.68481	0.0337*
H25	0.32047	0.48804	0.97322	0.0385*
H4	0.12896	0.76008	0.67241	0.0317*
H5C	−0.15805	0.46729	0.92075	0.0329*
H26	0.38949	0.05396	0.60649	0.0401*
H6B	−0.05285	0.61312	0.92131	0.0329*
H7A	0.02902	0.44235	0.9412	0.0329*
H8	0.07957	0.01854	0.95149	0.0333*
H9	0.12243	−0.23709	1.00075	0.0370*
H10	0.41592	−0.06346	0.81974	0.0312*
H11	0.45427	−0.31402	0.8739	0.0330*
H12	0.59537	0.7028	0.60182	0.0363*
H13	0.75282	0.80224	0.659	0.0473*
H14	0.70869	0.70983	0.75891	0.0439*
H15	0.49388	0.53435	0.80057	0.0350*
H16B	0.38648	0.61772	0.55362	0.0349*
H17A	0.2927	0.45945	0.56184	0.0349*
H18C	0.49271	0.45663	0.56808	0.0349*
H19	−0.07407	0.26017	0.58795	0.0319*
H20	−0.29926	0.1537	0.561	0.0358*
H21	−0.35117	0.22499	0.74466	0.0280*
H22	−0.56868	0.11802	0.7132	0.0315*
H23	0.15861	−0.17759	0.56312	0.0320*
H24	0.31469	0.14613	1.05021	0.0285*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0421 (2)	0.02082 (19)	0.0378 (2)	−0.00217 (16)	0.00356 (18)	−0.00364 (16)
Br2	0.0364 (2)	0.02332 (19)	0.02352 (18)	0.00005 (15)	0.00553 (15)	−0.00413 (14)
Ni1	0.0290 (2)	0.0171 (2)	0.0152 (2)	0.00158 (18)	−0.00022 (17)	−0.00274 (16)
O1	0.0351 (14)	0.0193 (12)	0.0176 (11)	0.0045 (10)	0.0019 (10)	−0.0031 (9)
O2	0.0299 (13)	0.0218 (12)	0.0179 (11)	−0.0006 (10)	0.0003 (10)	−0.0045 (10)
O3	0.0476 (16)	0.0161 (12)	0.0278 (13)	0.0055 (12)	0.0054 (12)	−0.0038 (10)
O4	0.0522 (18)	0.0197 (13)	0.0363 (15)	0.0025 (12)	0.0146 (14)	−0.0004 (12)
O5	0.0342 (15)	0.0445 (16)	0.0210 (12)	−0.0107 (13)	−0.0038 (11)	−0.0044 (12)
O6	0.0393 (16)	0.0491 (18)	0.0258 (13)	−0.0160 (14)	−0.0021 (12)	−0.0004 (13)
N1	0.0258 (15)	0.0195 (14)	0.0189 (13)	0.0014 (12)	−0.0010 (12)	−0.0039 (11)
N2	0.0245 (15)	0.0157 (13)	0.0175 (13)	−0.0005 (11)	−0.0013 (11)	−0.0021 (11)
N3	0.0283 (15)	0.0148 (13)	0.0159 (13)	−0.0002 (12)	−0.0007 (11)	−0.0004 (11)
N4	0.0367 (18)	0.0179 (14)	0.0275 (15)	0.0020 (13)	−0.0031 (14)	−0.0036 (12)
N5	0.0259 (15)	0.0206 (14)	0.0217 (14)	0.0047 (12)	−0.0029 (12)	−0.0049 (12)
N6	0.0244 (15)	0.0191 (14)	0.0164 (13)	0.0043 (12)	−0.0006 (11)	−0.0026 (11)
N7	0.0266 (15)	0.0225 (14)	0.0173 (13)	0.0006 (12)	−0.0011 (12)	−0.0037 (11)
N8	0.0287 (16)	0.0276 (16)	0.0215 (14)	0.0007 (13)	−0.0018 (12)	−0.0057 (12)
C1	0.0215 (16)	0.0187 (16)	0.0200 (15)	−0.0002 (13)	−0.0012 (13)	−0.0052 (13)
C2	0.0281 (18)	0.0211 (17)	0.0241 (17)	0.0004 (14)	0.0027 (14)	−0.0063 (14)
C3	0.035 (2)	0.0180 (17)	0.0292 (18)	0.0049 (15)	−0.0018 (16)	−0.0063 (15)
C4	0.033 (2)	0.0217 (18)	0.0248 (18)	0.0036 (15)	−0.0010 (15)	0.0006 (14)
C5	0.0308 (19)	0.0233 (18)	0.0211 (17)	0.0041 (15)	0.0017 (15)	−0.0020 (14)
C6	0.0256 (17)	0.0180 (16)	0.0184 (15)	−0.0029 (14)	0.0019 (13)	−0.0043 (13)
C7	0.035 (2)	0.0220 (18)	0.0218 (17)	0.0014 (15)	0.0051 (15)	−0.0042 (14)
C8	0.0229 (17)	0.0190 (16)	0.0200 (16)	−0.0004 (14)	−0.0013 (13)	−0.0034 (13)
C9	0.0241 (17)	0.0182 (16)	0.0208 (16)	−0.0020 (14)	−0.0021 (13)	−0.0051 (13)
C10	0.035 (2)	0.0222 (18)	0.0251 (18)	0.0011 (15)	0.0012 (15)	−0.0066 (14)
C11	0.041 (2)	0.0214 (18)	0.0249 (18)	−0.0005 (16)	0.0032 (16)	0.0005 (15)
C12	0.034 (2)	0.0229 (18)	0.0210 (17)	−0.0011 (15)	−0.0023 (15)	−0.0060 (14)
C13	0.033 (2)	0.0233 (18)	0.0285 (18)	0.0050 (15)	−0.0060 (16)	−0.0106 (15)
C14	0.0260 (18)	0.0210 (17)	0.0207 (16)	0.0045 (14)	0.0005 (14)	−0.0042 (14)
C15	0.032 (2)	0.031 (2)	0.0248 (18)	−0.0023 (16)	0.0010 (16)	−0.0046 (16)
C16	0.031 (2)	0.045 (2)	0.042 (2)	−0.0127 (19)	0.0019 (18)	−0.010 (2)
C17	0.032 (2)	0.049 (3)	0.032 (2)	−0.0068 (19)	−0.0012 (17)	−0.0148 (19)
C18	0.031 (2)	0.033 (2)	0.0244 (18)	0.0048 (16)	−0.0049 (15)	−0.0091 (16)
C19	0.0244 (17)	0.0214 (17)	0.0184 (16)	0.0052 (14)	−0.0003 (13)	−0.0038 (13)
C20	0.033 (2)	0.032 (2)	0.0195 (17)	−0.0017 (16)	0.0017 (15)	−0.0043 (15)
C21	0.0292 (18)	0.0149 (15)	0.0209 (16)	0.0051 (14)	−0.0008 (14)	−0.0031 (13)
C22	0.0263 (18)	0.0161 (16)	0.0210 (16)	0.0041 (14)	−0.0010 (14)	−0.0045 (13)
C23	0.0277 (18)	0.0303 (19)	0.0202 (16)	0.0013 (15)	0.0037 (14)	−0.0076 (15)
C24	0.034 (2)	0.039 (2)	0.0184 (16)	0.0008 (17)	−0.0017 (15)	−0.0106 (16)
C25	0.0300 (18)	0.0196 (17)	0.0186 (16)	0.0046 (14)	−0.0011 (14)	−0.0042 (13)
C26	0.0282 (19)	0.0246 (18)	0.0225 (17)	0.0030 (15)	−0.0000 (14)	−0.0024 (14)
C27	0.033 (2)	0.0277 (19)	0.0251 (18)	−0.0006 (16)	−0.0020 (16)	−0.0074 (15)
C28	0.0291 (18)	0.0257 (18)	0.0173 (16)	−0.0005 (15)	0.0004 (14)	−0.0055 (14)
C29	0.033 (2)	0.0238 (18)	0.0199 (16)	0.0031 (15)	−0.0004 (15)	−0.0018 (14)
C30	0.0312 (19)	0.0193 (16)	0.0196 (16)	−0.0017 (14)	0.0052 (14)	−0.0031 (13)
C31	0.0258 (17)	0.0213 (17)	0.0191 (15)	0.0005 (14)	−0.0003 (13)	−0.0071 (13)
C32	0.0287 (18)	0.0232 (17)	0.0201 (16)	−0.0003 (14)	−0.0010 (14)	−0.0077 (14)
C33	0.0276 (18)	0.0188 (16)	0.0201 (16)	−0.0018 (14)	−0.0027 (14)	−0.0049 (13)
C34	0.0311 (19)	0.0182 (17)	0.0254 (17)	0.0026 (15)	−0.0055 (15)	−0.0050 (14)

Geometric parameters (Å, º)

Br1—C30	1.890 (3)	C16—C17	1.373 (6)
Br2—C31	1.906 (3)	C17—C18	1.392 (5)
Ni1—O1	2.079 (2)	C19—C20	1.488 (5)
Ni1—O2	2.118 (3)	C21—C22	1.506 (5)
Ni1—N1	2.110 (3)	C22—C23	1.395 (5)
Ni1—N2	1.986 (3)	C22—C25	1.394 (5)
Ni1—N5	2.116 (3)	C23—C24	1.378 (6)
Ni1—N6	1.983 (3)	C25—C26	1.385 (6)
O1—C8	1.272 (4)	C27—C28	1.508 (6)
O2—C21	1.279 (4)	C28—C29	1.399 (5)
C34—O3	1.324 (4)	C28—C30	1.391 (5)
C34—O4	1.207 (4)	C29—C30^i	1.388 (6)
C27—O5	1.300 (4)	C31—C32^ii	1.385 (5)
C27—O6	1.223 (4)	C31—C33	1.394 (5)
N1—C1	1.354 (5)	C32—C33	1.406 (4)
N1—C5	1.339 (4)	C33—C34	1.509 (5)
N2—N3	1.380 (3)	O3—H25	0.840
N2—C6	1.290 (4)	O5—H26	0.840
N3—C8	1.337 (5)	C2—H1	0.950
N4—C11	1.339 (5)	C3—H2	0.950
N4—C13	1.338 (4)	C4—H3	0.950
N5—C14	1.364 (4)	C5—H4	0.950
N5—C18	1.340 (5)	C7—H5C	0.980
N6—N7	1.380 (4)	C7—H6B	0.980
N6—C19	1.297 (4)	C7—H7A	0.980
N7—C21	1.332 (4)	C10—H8	0.950
N8—C24	1.343 (4)	C11—H9	0.950
N8—C26	1.344 (5)	C12—H10	0.950
C1—C2	1.391 (5)	C13—H11	0.950
C1—C6	1.484 (4)	C15—H12	0.950
C2—C3	1.394 (4)	C16—H13	0.950
C3—C4	1.379 (5)	C17—H14	0.950
C4—C5	1.392 (5)	C18—H15	0.950
C6—C7	1.485 (5)	C20—H16B	0.980
C8—C9	1.499 (4)	C20—H17A	0.980
C9—C10	1.391 (4)	C20—H18C	0.980
C9—C12	1.383 (5)	C23—H19	0.950
C10—C11	1.387 (5)	C24—H20	0.950
C12—C13	1.384 (5)	C25—H21	0.950
C14—C15	1.394 (5)	C26—H22	0.950
C14—C19	1.482 (6)	C29—H23	0.950
C15—C16	1.387 (7)	C32—H24	0.950
O1—Ni1—O2	90.25 (9)	N8—C26—C25	122.2 (3)
O1—Ni1—N1	154.75 (11)	O5—C27—O6	126.1 (4)
O1—Ni1—N2	77.64 (10)	O5—C27—C28	111.6 (3)
O1—Ni1—N5	96.88 (10)	O6—C27—C28	122.3 (3)
O1—Ni1—N6	103.71 (11)	C27—C28—C29	118.1 (3)
O2—Ni1—N1	97.70 (11)	C27—C28—C30	124.1 (3)
O2—Ni1—N2	97.26 (10)	C29—C28—C30	117.7 (4)
O2—Ni1—N5	155.41 (10)	C28—C29—C30^i	121.3 (3)
O2—Ni1—N6	77.36 (10)	Br1—C30—C28	122.5 (3)
N1—Ni1—N2	77.60 (11)	Br1—C30—C29^i	116.2 (2)
N1—Ni1—N5	85.78 (11)	C28—C30—C29^i	121.1 (3)
N1—Ni1—N6	101.41 (11)	Br2—C31—C32^ii	115.4 (3)
N2—Ni1—N5	107.23 (12)	Br2—C31—C33	123.7 (2)
N2—Ni1—N6	174.40 (12)	C32^ii—C31—C33	121.0 (3)
N5—Ni1—N6	78.10 (12)	C31^ii—C32—C33	121.9 (3)
Ni1—O1—C8	108.6 (2)	C31—C33—C32	117.1 (3)
Ni1—O2—C21	107.8 (2)	C31—C33—C34	124.0 (3)
Ni1—N1—C1	112.86 (19)	C32—C33—C34	118.8 (3)
Ni1—N1—C5	127.7 (2)	O3—C34—O4	123.7 (3)
C1—N1—C5	118.7 (3)	O3—C34—C33	112.6 (3)
Ni1—N2—N3	117.9 (2)	O4—C34—C33	123.7 (3)
Ni1—N2—C6	120.5 (2)	C34—O3—H25	109.465
N3—N2—C6	120.7 (3)	C27—O5—H26	109.470
N2—N3—C8	107.6 (2)	C1—C2—H1	120.447
C11—N4—C13	117.1 (3)	C3—C2—H1	120.444
Ni1—N5—C14	110.8 (2)	C2—C3—H2	120.318
Ni1—N5—C18	127.9 (2)	C4—C3—H2	120.314
C14—N5—C18	118.8 (3)	C3—C4—H3	120.872
Ni1—N6—N7	118.25 (18)	C5—C4—H3	120.856
Ni1—N6—C19	120.4 (3)	N1—C5—H4	118.484
N7—N6—C19	121.3 (3)	C4—C5—H4	118.485
N6—N7—C21	108.4 (3)	C6—C7—H5C	109.473
C24—N8—C26	118.2 (3)	C6—C7—H6B	109.467
N1—C1—C2	121.4 (3)	C6—C7—H7A	109.477
N1—C1—C6	114.9 (3)	H5C—C7—H6B	109.476
C2—C1—C6	123.6 (3)	H5C—C7—H7A	109.472
C1—C2—C3	119.1 (3)	H6B—C7—H7A	109.463
C2—C3—C4	119.4 (3)	C9—C10—H8	120.656
C3—C4—C5	118.3 (3)	C11—C10—H8	120.656
N1—C5—C4	123.0 (3)	N4—C11—H9	118.224
N2—C6—C1	113.0 (3)	C10—C11—H9	118.224
N2—C6—C7	124.4 (3)	C9—C12—H10	120.307
C1—C6—C7	122.5 (3)	C13—C12—H10	120.297
O1—C8—N3	127.7 (3)	N4—C13—H11	118.377
O1—C8—C9	117.4 (3)	C12—C13—H11	118.380
N3—C8—C9	114.9 (3)	C14—C15—H12	120.593
C8—C9—C10	121.0 (3)	C16—C15—H12	120.579
C8—C9—C12	120.9 (3)	C15—C16—H13	120.167
C10—C9—C12	118.0 (3)	C17—C16—H13	120.138
C9—C10—C11	118.7 (3)	C16—C17—H14	120.526
N4—C11—C10	123.6 (3)	C18—C17—H14	120.526
C9—C12—C13	119.4 (3)	N5—C18—H15	118.856
N4—C13—C12	123.2 (3)	C17—C18—H15	118.858
N5—C14—C15	121.4 (4)	C19—C20—H16B	109.483
N5—C14—C19	115.4 (3)	C19—C20—H17A	109.479
C15—C14—C19	123.3 (3)	C19—C20—H18C	109.470
C14—C15—C16	118.8 (3)	H16B—C20—H17A	109.459
C15—C16—C17	119.7 (4)	H16B—C20—H18C	109.470
C16—C17—C18	118.9 (4)	H17A—C20—H18C	109.466
N5—C18—C17	122.3 (3)	C22—C23—H19	120.672
N6—C19—C14	112.8 (3)	C24—C23—H19	120.657
N6—C19—C20	125.3 (4)	N8—C24—H20	118.393
C14—C19—C20	121.9 (3)	C23—C24—H20	118.385
O2—C21—N7	127.6 (3)	C22—C25—H21	120.311
O2—C21—C22	118.3 (3)	C26—C25—H21	120.324
N7—C21—C22	114.1 (3)	N8—C26—H22	118.897
C21—C22—C23	120.6 (3)	C25—C26—H22	118.896
C21—C22—C25	121.1 (3)	C28—C29—H23	119.375
C23—C22—C25	118.3 (3)	C30^i—C29—H23	119.374
C22—C23—C24	118.7 (3)	C31^ii—C32—H24	119.053
N8—C24—C23	123.2 (4)	C33—C32—H24	119.046
C22—C25—C26	119.4 (3)
O1—Ni1—O2—C21	−98.39 (14)	Ni1—N6—N7—C21	7.7 (3)
O2—Ni1—O1—C8	−91.08 (16)	Ni1—N6—C19—C14	−1.8 (3)
O1—Ni1—N1—C1	−13.5 (4)	Ni1—N6—C19—C20	177.56 (19)
O1—Ni1—N1—C5	156.50 (19)	N7—N6—C19—C14	178.4 (2)
N1—Ni1—O1—C8	17.8 (3)	N7—N6—C19—C20	−2.2 (5)
O1—Ni1—N2—N3	−7.43 (18)	C19—N6—N7—C21	−172.6 (3)
O1—Ni1—N2—C6	−176.7 (2)	N6—N7—C21—O2	−2.2 (4)
N2—Ni1—O1—C8	6.30 (16)	N6—N7—C21—C22	178.0 (2)
O1—Ni1—N5—C14	115.31 (17)	C24—N8—C26—C25	0.2 (5)
O1—Ni1—N5—C18	−83.1 (2)	C26—N8—C24—C23	−0.0 (5)
N5—Ni1—O1—C8	112.50 (17)	N1—C1—C2—C3	−3.3 (5)
O1—Ni1—N6—N7	79.58 (19)	N1—C1—C6—N2	9.9 (4)
O1—Ni1—N6—C19	−100.16 (19)	N1—C1—C6—C7	−170.5 (3)
N6—Ni1—O1—C8	−168.13 (16)	C2—C1—C6—N2	−167.5 (3)
O2—Ni1—N1—C1	93.81 (18)	C2—C1—C6—C7	12.1 (5)
O2—Ni1—N1—C5	−96.2 (2)	C6—C1—C2—C3	173.9 (3)
N1—Ni1—O2—C21	105.65 (14)	C1—C2—C3—C4	0.6 (5)
O2—Ni1—N2—N3	81.23 (19)	C2—C3—C4—C5	2.1 (5)
O2—Ni1—N2—C6	−88.0 (2)	C3—C4—C5—N1	−2.5 (6)
N2—Ni1—O2—C21	−175.96 (14)	O1—C8—C9—C10	−161.1 (3)
O2—Ni1—N5—C14	9.4 (4)	O1—C8—C9—C12	16.4 (5)
O2—Ni1—N5—C18	171.00 (16)	N3—C8—C9—C10	17.2 (5)
N5—Ni1—O2—C21	8.9 (3)	N3—C8—C9—C12	−165.3 (3)
O2—Ni1—N6—N7	−7.56 (16)	C8—C9—C10—C11	177.1 (3)
O2—Ni1—N6—C19	172.7 (2)	C8—C9—C12—C13	−178.0 (3)
N6—Ni1—O2—C21	5.61 (14)	C10—C9—C12—C13	−0.4 (5)
N1—Ni1—N2—N3	177.6 (2)	C12—C9—C10—C11	−0.5 (5)
N1—Ni1—N2—C6	8.3 (2)	C9—C10—C11—N4	0.5 (6)
N2—Ni1—N1—C1	−1.98 (18)	C9—C12—C13—N4	1.5 (6)
N2—Ni1—N1—C5	168.0 (3)	N5—C14—C15—C16	0.4 (5)
N1—Ni1—N5—C14	−89.92 (18)	N5—C14—C19—N6	13.5 (4)
N1—Ni1—N5—C18	71.7 (2)	N5—C14—C19—C20	−165.9 (3)
N5—Ni1—N1—C1	−110.67 (19)	C15—C14—C19—N6	−165.1 (3)
N5—Ni1—N1—C5	59.3 (2)	C15—C14—C19—C20	15.5 (5)
N1—Ni1—N6—N7	−103.00 (18)	C19—C14—C15—C16	178.9 (3)
N1—Ni1—N6—C19	77.3 (2)	C14—C15—C16—C17	2.2 (6)
N6—Ni1—N1—C1	172.39 (18)	C15—C16—C17—C18	−2.6 (6)
N6—Ni1—N1—C5	−17.6 (3)	C16—C17—C18—N5	0.5 (6)
N2—Ni1—N5—C14	−165.54 (16)	O2—C21—C22—C23	−176.1 (2)
N2—Ni1—N5—C18	−3.9 (2)	O2—C21—C22—C25	3.5 (4)
N5—Ni1—N2—N3	−100.89 (19)	N7—C21—C22—C23	3.7 (4)
N5—Ni1—N2—C6	89.8 (2)	N7—C21—C22—C25	−176.7 (2)
N5—Ni1—N6—N7	173.9 (2)	C21—C22—C23—C24	179.7 (3)
N5—Ni1—N6—C19	−5.89 (18)	C21—C22—C25—C26	−179.6 (2)
N6—Ni1—N5—C14	12.69 (16)	C23—C22—C25—C26	0.0 (4)
N6—Ni1—N5—C18	174.3 (2)	C25—C22—C23—C24	0.1 (4)
Ni1—O1—C8—N3	−5.3 (4)	C22—C23—C24—N8	−0.1 (5)
Ni1—O1—C8—C9	172.72 (19)	C22—C25—C26—N8	−0.2 (5)
Ni1—O2—C21—N7	−3.6 (4)	O5—C27—C28—C29	−43.0 (4)
Ni1—O2—C21—C22	176.19 (17)	O5—C27—C28—C30	139.8 (3)
Ni1—N1—C1—C2	174.0 (2)	O6—C27—C28—C29	136.1 (3)
Ni1—N1—C1—C6	−3.4 (3)	O6—C27—C28—C30	−41.1 (5)
Ni1—N1—C5—C4	−169.6 (2)	C27—C28—C29—C30^i	−177.8 (3)
C1—N1—C5—C4	−0.1 (5)	C27—C28—C30—Br1	−8.3 (5)
C5—N1—C1—C2	3.0 (5)	C27—C28—C30—C29^i	177.6 (3)
C5—N1—C1—C6	−174.4 (3)	C29—C28—C30—Br1	174.6 (3)
Ni1—N2—N3—C8	6.7 (3)	C29—C28—C30—C29^i	0.4 (5)
Ni1—N2—C6—C1	−12.3 (4)	C30—C28—C29—C30^i	−0.4 (5)
Ni1—N2—C6—C7	168.1 (2)	C28—C29—C30^i—Br1^i	174.9 (3)
N3—N2—C6—C1	178.7 (3)	C28—C29—C30^i—C28^i	0.5 (5)
N3—N2—C6—C7	−0.9 (5)	Br2—C31—C32^ii—C33^ii	179.7 (2)
C6—N2—N3—C8	176.0 (3)	Br2—C31—C33—C32	−179.7 (2)
N2—N3—C8—O1	−0.5 (5)	Br2—C31—C33—C34	−1.8 (5)
N2—N3—C8—C9	−178.5 (2)	C32^ii—C31—C33—C32	−0.2 (5)
C11—N4—C13—C12	−1.5 (6)	C32^ii—C31—C33—C34	177.7 (3)
C13—N4—C11—C10	0.5 (6)	C33—C31—C32^ii—C33^ii	0.2 (6)
Ni1—N5—C14—C15	161.1 (2)	C31^ii—C32—C33—C31	0.2 (5)
Ni1—N5—C14—C19	−17.6 (3)	C31^ii—C32—C33—C34	−177.8 (3)
Ni1—N5—C18—C17	−158.3 (2)	C31—C33—C34—O3	177.0 (3)
C14—N5—C18—C17	2.0 (5)	C31—C33—C34—O4	−4.1 (6)
C18—N5—C14—C15	−2.4 (5)	C32—C33—C34—O3	−5.2 (5)
C18—N5—C14—C19	178.9 (3)	C32—C33—C34—O4	173.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H25···N4^iii	0.84	1.87	2.706 (4)	178
O5—H26···N8^iv	0.84	1.72	2.557 (4)	172

Symmetry codes: (iii) x, y+1, z; (iv) x+1, y, z.